1 Merged

Journal of Alloys and Compounds 731 (2018) 955e963
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Journal of Alloys and Compounds

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Review
Characterization of a sodium molybdate compound b-Na4Cu(MoO4)3

Wassim Dridi a, *, Mohamed Faouzi Zid a, Miroslaw Maczka b
a
University of Tunis El Manar, Faculty of Sciences of Tunis, Laboratory of Materials, Crystallochemistry and Applied Thermodynamics, El Manar II, 2092,
Tunis, Tunisia
b
Institute of Low Temperature and Structure Research, Polish Academy of Sciences, P.O. Box 1410, 50-950 Wrocław 2, Poland
a r t i c l e i n f o a b s t r a c t
Article history: The complex impedance of b-Na4Cu(MoO4)3 was investigated in the 573e833 K temperature range and
Received 10 August 2017 40 Hze5 MHz frequency range. The Nyquist plots have been successfully analysed by an equivalent of
Accepted 15 October 2017 series combination of grains and grain boundaries elements. This analysis revealed presence of two
Available online 16 October 2017
relaxation phenomena and revealed that grain boundaries cause a partial blockage of the carriers charge.
We have also measured Raman and IR spectra. Based on C2h factor group symmetry and the correlation
Keywords:
method, the number and type of intramolecular vibrations have been predicted. We have also proposed
Conductivity
assignment of the observed vibrational modes. Band gap energies were also determined by different
Raman
Infrared
methods using UVeviseNIR diffuse reflectance spectrum. The obtained values shows that this material is
Molybdate a semiconductor with indirect band gap. Absorption spectrum showed presence of two strong bands. The
Band gap band around 1.38 eV has been assigned to the forbidden ded transitions of Cu2þ ion adopting the [4 þ 2]
Jahn-Teller distortion whereas that extending from 2.15 to 4.13 eV has been attributed to ligand to metal
charge transfer transition.
© 2017 Elsevier B.V. All rights reserved.
Contents
1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 955
2. Materials and methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 956
2.1. Synthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 956
2.2. Characterization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 956
3. Results and discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 956
3.1. Structure description . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 956
3.2. Complex impedance studies of b-Na4Cu(MoO4)3 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 957
3.3. Raman and IR studies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 958
3.4. Optical studies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 960
4. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 961
Conflict of interest . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 962
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 962
1. Introduction importance in the current technology, especially in the context of

environment friendly applications. To improve efficiency and
Energy storage devices such as batteries gain increasing durability of energy storage devices, there is a need to develop new
solid electrolytes. The design of new solid state electrolytes should
take into account not only their efficiency but also economic and
ecological issues. It is well known that one of the paramount
* Corresponding author. properties necessary for new materials to be good candidates for
E-mail addresses: wassimdridi35@yahoo.fr (W. Dridi), faouzi_zid@yahoo.fr
solid electrolytes is presence of good ionic conduction. In that
(M.F. Zid), m.maczka@int.pan.wroc.pl (M. Maczka).
https://doi.org/10.1016/j.jallcom.2017.10.111
0925-8388/© 2017 Elsevier B.V. All rights reserved.
956 W. Dridi et al. / Journal of Alloys and Compounds 731 (2018) 955e963
respect, a very exhaustive studies carried out by many scientists in

recent years, have led to the discovery of new ionic conductors with
lithium ions such as Li2-2xMg2þx(MoO4)3, Li3M(MoO4)3 (MIII ¼ Cr,
Fe) [1] and Li2Cu2(MoO4)3 [2]. However, bearing in mind that so-
dium is very abundant and therefore inexpensive, the next chal-
lenge for energy storage will be to find new structures and new
ionic conductors containing Naþ cations as mobile species. One of
such Naþ-based group of ionic conductors constitute sodium mo-
lybdates, especially those with alluaudite-type structure, which
exhibit remarkable ionic conduction properties due to presence of
large tunnels occupied by the mobile monovalent cations. For
example, for Na25Cs8Fe5(MoO4)24 compound conductivity s is
about 102e103 S cm1 at 642 K [3].
Among different transition metal ions that can be employed in a
synthesis of inorganic or hybrid organic-inorganic materials, Cu2þ
ions are especially interesting since Jahn-Teller effect of these ions
often results in different structures compared to other analogues
with divalent cations that do not exhibit Jahn-Teller effect, such as
Mn2þ, Co2þ, Fe2þ etc. [4,5]. It is also worth adding that some ma-
terials containing CueO bonds in copper-oxygen ceramic systems Fig. 1. Calculated and experimental X-ray powder diffraction patterns of b-
Na4Cu(MoO4)3.
are characterized by high-temperature superconductivity, which
has resulted in broad interest in their structural and physico-
chemical properties [6]. Regarding molybdates, they found appli- 2.2. Characterization
cations as laser materials [7] and selective catalysts for the oxida-
tion of hydrocarbons [8e11]. For the electric characterization, a pellet of approximately
Encouraged by interesting properties of some sodium molyb- 1.25 cm2 in surface and 0.22 cm in thickness was prepared by
dates and materials containing Cu2þ ions, we have decided to study isostatic pressing at 4 kbar and sintering at 773 K for 24 h in air with
alluaudite-type b-Na4Cu(MoO4)3 molybdate. In particular, the 10 K,min1 heating and cooling rates. It has a geometric factor of e/
present study is aimed at interpreting the electrical response of the s ¼ 0.176 cm1. The measurements were carried out in air in the
grain and grains boundaries effects of b-Na4Cu(MoO4)3, which frequency range from 40 to 5 MHz and in the temperature range
enormously influences the electrical properties. Our aim is also to from 653 K to 833 K. Two platinum electrodes were used as ion-
determine the band gap energy, which is an important feature of blocking electrodes. In order to ensure good electrical contact, a
semiconductor materials that determines their applications in platinum deposit was produced by sputtering on each face of the
photoconductivity and electroluminescence [12]. Finally, we have pellet. Since after rise of the temperature by 20 C, the system
also decided to study phonon properties of b-Na4Cu(MoO4)3 in became stationary after about 30 min, each measurement was
order to obtain deeper insight into the molecular structure at performed using a 20 C temperature interval and waiting time of
microscopic level. We employed for this purpose infrared and 30 min. Complex impedance spectroscopy makes it possible to
Raman spectroscopic methods since they are sensitive for order/ study the electrical properties of materials by showing separately
disorder effects, changes in coordination of molybdenum ions and the resistive contributions of the different electrical phenomena of
changes in strength of interactions between various molybdenum- the material, the slow one at low frequencies and the fast one at
oxygen polyhedra [13e20]. high frequencies.
The diffuse reflectance measurements were carried out at room
temperature by using Perkin Elmer (lambda 900) UV-VIS-IR spec-
trometer. The measurements were performed on powders in the
300e1800 nm wavelength range.
2. Materials and methods Raman spectrum of the pellet sample was collected using a LAB
RAMAN HR800 spectrometer. The wavenumber range was from
2.1. Synthesis 100 to 1100 cm1 and the spectral resolution was 2 cm1. The
632.81 nm line was used as excitation and a power was adjusted to
Traditional solid state reaction technique was used for the 1 mW in order to avoid heating and degradation of the sample.
synthesis of b-Na4Cu(MoO4)3 crystallized powders. The starting Room-temperature IR spectrum in the 400-1100 cm1 range
materials (NaNO3, Cu(NO3)2 and MoO3), taken in stoichiometric was recorded using Thermo Scientific Nicolet iS50 FT-IR spec-
proportions, were intimately mixed in an agate mortar. This trometer. The spectral resolution was 2 cm1.
mixture was annealed in a platinum crucible at 300 C for 4 h in
order to decompose the nitrates and get rid of the volatile products.
The obtained powder was then pelletized using a uniaxial press, 3. Results and discussion
and heated in porcelain crucible with a rate of 50 C per hour to
500 C. Finally, the sample was slowly cooled down to room tem- 3.1. Structure description
perature. The phase purity of the obtained sample was checked by
X-ray powder diffraction using a PAN-analytical X'Pert PRO X-ray b-Na4Cu(MoO4)3 crystallizes in the monoclinic space group C2/c
diffractometer equipped with copper anticathode (lKa ¼ 1.5406 Å). with the lattice parameters a ¼ 12.5318 (9) Å, b ¼ 13.8181 (9) Å,
Fig. 1 shows that the experimental XRD pattern is in good agree- c ¼ 7.1159 (7) Å, b ¼ 111.95 (2) , V ¼ 1142.9 (2) (Å3), Z ¼ 4 [21]. The
ment with the calculated one and some differences in peak in- Cu2þ and Naþ cations are located at the same general site with
tensities are believed to be caused by a preferential orientation of occupancies of 0.5. All atoms are on general positions, except of
the crystallites. Mo2, Na2, Na3 and Na4. One O atom is split into two separate
W. Dridi et al. / Journal of Alloys and Compounds 731 (2018) 955e963 957
positions with the occupancies of 0.5. This compound adopts the

alluaudite-type structure characterized by distorted CuO6 octa-
hedra [21]. It is worth adding that molybdate compounds with
alkali metal ions are often characterized by structural cation dis-
order, which shows possibility of ionic conductivity in these sys-
tems [22,23].
3.2. Complex impedance studies of b-Na4Cu(MoO4)3
Fig. 2 shows the Nyquist diagrams of b-Na4Cu(MoO4)3 in the

573e753 K temperature range. The evolution of these curves with
temperature shows the thermal behavior of the studied material
resistance. Generally, the frequency variation of the complex
impedance takes the form of a semicircle whose intersection with
the axis of the real part gives the resistance of the system. Each
diagram presented in Fig. 2 shows presence of two entangled
semicircle that indicate presence of two relaxations. The first arc,
existing towards higher frequencies, corresponds to mobility of
ions through the grains. This contribution represents intrinsic
conduction and produces an intra-granular resistance. The second
arc, noted at lower frequencies, represents the ions displacement
through the grains boundaries [24,25]. In each temperature, the
diagrams are studied using the same equivalent circuit represent-
ing these two relaxations constituted by two cells disposed in se-
ries, composed by the parallel connection of the following: Rg jj C1
and Rgb jj CPE1. This circuit is also used by several author cited in the
paper of Mahamoud et al. [24]. Rg and Rgb are the resistances of
grains and grains' boundaries, respectively. C1 is the pure capaci-
tance of grain and CPE1 represents the fractal capacitance constant
phase element corresponding to the grains boundaries. The simi-
larity between the calculated and experimental curves (fit) con-
firms the validity of the modeled equivalent circuit. The total
resistance Rtotal of the sample is obtained from the intersection of
the semicircle on the low frequency side with the real axis (Z0 ). We
have used Zview software to fit these curves. The value of Rtotal
follows from the relation: Rtotal ¼ Rg þ Rgb. The electrical parame-
ters of our sample are presented in Table 1.
Conductivity values si are determined from the resistance Ri of
each phenomenon and from the form factor (e/s) of the pellet using
the equation [26]:
si ¼ e/Ri.s (1)
The values of ionic conductivities of b-Na4Cu(MoO4)3 are rep-

resented in Table 2. Fig. 3 shows that si follows the well known
Arrhenius relationship:

Ea
sT ¼ s0 exp (2)
kb T
The values of the activation energies are shown in Table 3.
It is worth noting that in the 573e793 K range the total con-
ductivity of b-Na4Cu(MoO4)3 is greater than conductivity related to
the grain boundaries conductivity but lower than conductivity
related to the grains. This behavior can be explained by the pres-
ence of a partial blockage of carrier charges caused by the grain
boundaries [27]. As a result, the conductivity of b-Na4Cu(MoO4)3 is
reduced by the low conductivity of the grain boundaries. According
to the literature, microstructural defects such as grain boundaries,
cracks and pores can cause blockage of the ionic carriers in the
internal interfaces. This phenomenon is visualized in the imped-
ance spectroscopy as a semicircle separated from the lower fre-
Fig. 2. Complex impedance spectrum of b-Na4Cu(MoO4)3 over temperature range quency side [28]. The blocking of the ions by the pores can be
from 573 K to 753 K. quantitatively characterized by the blocking factor a using the
following equation [29,30]:
Table 1 Table 3
Simulated data of the electrical parameters for the proposed equivalent circuit. Activation energies in b-Na4Cu(MoO4)3.
T (K) Rg (U) Cg (F) Rjg (U) Cgb (F) S Ri Contribution Temperature range (K) Ea (eV)
573 503570 2.1791011 1.0183107 7.0291011 1.0680107 Grains 573e693 1.36

593 294840 2.0431011 4.5657106 6.6411011 4.8600106 693e733 0.66
613 137270 1.7161011 2.1325106 6.8891011 2.2690106 733e833 0.11
633 69505 1.5491011 1.0292106 7.1081011 1.0980106 Grains boundaries 573e833 1.59
653 27687 1.2831011 4.0419105 7.8401011 4.3187105 Total 573e833 1.44
673 10289 9.2891012 1.3376105 9.5031011 1.4404105
693 6102 8.4091012 5.9633104 1.0441010 6.5735104
713 4567 7.8731012 3.4514104 1.0331010 3.9081104
733 3569 7.1521012 2.0348104 1.0311010 2.3917104 3.3. Raman and IR studies
753 2670 6.8591012 1.0463104 1.0051010 1.3133104
773 2150 6.6431012 5.1810103 1.0621010 7.3310103 As mentioned above, b-Na4Cu(MoO4)3 crystallizes in the
793 2094 6.7171012 2.6460103 9.8641011 4.7400103
monoclinic space group C2/c which corresponds to C2h factor
813 2066 6.6461012 1.1780103 1.3451010 3.2440103
833 2050 6.7331012 6.9070102 1.5561010 2.7407103 group. The number of molecules per primitive Bravais cell ZB is two.
Mo1, Na1 and the six oxygen atoms occupy sites of C1 symmetry,
Na2, Na4 and Mo3 atoms occupy sites of C2 symmetry whereas Na3
atom occupies the Ci symmetry site. The total number of atoms in
Table 2
Values of ionic conductivities of b-Na4Cu(MoO4)3 as a function of temperature. the primitive cell is 40 and this gives 120 zone center vibrational
degrees of freedom. In order to assign the vibrational modes, it is
T (K) Conductivities (U cm1)
necessary to measure both Raman and IR spectra beacuse for the
sg sbg stotal centrosymmetric structure no modes can be both Raman- and IR-
573 3.495107 1.728108 1.646108 active according to the rule of mutual exclusion [31]. We have
593 5.969107 3.854108 3.621108 calculated the crystal vibrational modes using group theoretical
613 1.280106 8.250108 7.754108 approach developed by Fateley et al. [32]. To perform these calcu-
633 2.532106 1.710107 1.601107
lation, we had taken into account limited validity of this method in
653 6.356106 4.354107 4.075107
673 1.710105 1.315106 1.221106 case of disorder in crystals [33]. Consequently, we used only com-
693 2.884105 2.951106 2.677106 plete atoms and not splitted ones. The results of the factor group
713 3.853105 5.099106 4.503106 analysis for b-Na4Cu(MoO4)3 are represented in Table 4. The
733 4.931105 8.649106 7.358106 vibrational representation of the C2/c structure of b-
753 6.591105 1.682105 1.340105
773 8.186105 3.397105 2.400105
Na4Cu(MoO4)3 at the Brillouin zone center has the form:
793 8.404105 6.651105 3.713105
813 8.518105 1.494104 5.425105 Gvibr ¼ 27Ag þ 27Bg þ 33Au þ 33Bu
833 8.585105 2.548104 6.421105
Among these modes, (3N-3) modes are optical and 3 acoustic,
where N is the number of the unit cell atoms [34]:
Gacoustic ¼ 1Auþ 2Bu
Goptic ¼ 27Ag þ 27Bg þ 32Au þ 31Bu
All Ag and Bg modes are Raman-active whereas Au and Bu modes

are IR-active.
The vibrational modes can be further subdivided into internal
modes of the MoO4 tetrahedra and lattice modes. The isolated
MoO24 ion has a Td symmetry and four internal modes: n1(A1)
nondegenerate symmetric stretching mode at 936 cm1, n2(E)
doubly degenerate symmetric bending mode at 220 cm1, n3(F2)
triply degenerate asymmetric stretching mode at 895 cm1 and
n4(F2) triply degenerate asymmetric bending mode at 365 cm1
[35]. All four vibrational modes are Raman-active whereas only F2
symmetry modes are IR-active. When MoO2 4 ion is placed in the
crystal lattice, its symmetry is reduced due to the restriction
established by the lattice. In the structure of b-Na4Cu(MoO4)3, the
local symmetry of Mo1O4 and Mo2O4 tetrahedra decreases to C1
and C2, respectively. Tables 5 and 6 show the correlation schemes
between the point group of Td symmetry of the isolated MoO4, its
Fig. 3. Arrhenius plot of conductivity of b-Na4Cu(MoO4)3.
site-symmetries C1 and C2, and the factor group C2h. These tables
show that as a result of symmetry reduction, all internal modes
a¼ Rgb/RgbþRg (3) become Raman- and IR-active. Furthermore, the degeneracy of
modes is lifted. In particular, the 36 internal vibrational modes of
Fig. 4 shows that the blocking effect of the blockers is dependent the Mo1O4 unit at C1 sites are:
on temperature. As a result, the increase in temperature leads to
reduction in the blocking effect by the grain boundaries. GMo1O4 ¼ 9A(R) (R) (IR)
g þ 9Bg þ 9Au þ 9B(IR)
u
Gn2 ¼ 2A(R) (R) (IR)

u
Gn3 ¼ 3A(R) (R) (IR)

u
Gn4 ¼ 3A(R) (R) (IR)

u
Where as 18 modes of the Mo2O4 unit at C2 sites are distributed as

follows:
GMo2O4 ¼ 5A(R) (R) (IR)

u
Gn1 ¼ A(R) (IR)

g þ Au
Gn2 ¼ 2A(R) (IR)

g þ 2Au
Gn3 ¼ Ag þ 2Bg þ Au þ2Bu
Gn4 ¼ Ag þ 2Bg þ Au þ2Bu
Regarding external modes of MoO4, they can be subdivided into

translational and librational modes [36]. These modes are distrib-
Fig. 4. Variation of the blockage factor a in the 573e793 K temperature range.
uted as follows:
Gn1 ¼ A(R) (R) (IR)

g þ Bg þ Au þ B(IR)
u
Gtransl Mo1O4 ¼ 3A(R) (R) (IR)
u
Table 4
Factor group analysis for the monoclinic phase of b-Na4Cu(MoO4)3.
P
Atoms Site symmetry ns tg g fg z Cz az Gatom
C2/c Gtransl Mo1, Cu1/Na1, 6 O C1 4 3 A (Tx, Ty, Tz) 12 Ag 1 3 8 (3Agþ3Bg þ3Auþ3Bu)
Z¼4 Bg 1 3
ZB ¼ 2 Au 1 3
Bu 1 3
Gtransl Na3 Ci 2 3 A (Tx, Ty, Tz) 6 Au 1 3 3Auþ3Bu
Bu 1 3
Gtransl Mo2, Na2, Na4 C2 2 1 A (Tz) 2 Ag 1 1 3(Ag þ Bgþ 2Au þ2Bu)
Bg 1 1
2 B (Tx, Ty) 4 Au 1 2
Bu 1 2
ZB: number of molecules per primitive Bravais cell, ns: number of positions, tg: number of translations of a site species g, fg: the degree of vibrational freedom present in each
site species g
Cz represents the degeneracy of the species z of the factor group, whereas az is the number of lattice vibrations of the equivalent set of atoms in species z of the factor group.
Table 5
Correlation scheme for the internal modes of Mo1O4 in b-Na4Cu(MoO4)3 structure.
Table 6
Correlation scheme for the internal modes of Mo2O4 in b-Na4Cu(MoO4)3 structure.
Gtransl Mo2O4 ¼ Ag(R) þ 2Bg(R) þ Au(IR) þ2Bu(IR)
Glibration Mo1O4 ¼ 3A(R) (R) (IR)

u
Glibration Mo2O4 ¼ Ag(R) þ 2Bg(R) þ Au(IR) þ2Bu(IR)
The presence of an inversion center in the b-Na4Cu(MoO4)3

structure is reflected by the fact that IR and Raman modes are
observed at different wavenumbers (Fig. 5, Table 7). Regarding
assignment of vibrational modes, it is often difficult for alluaudite-
type structures because of the cationic disorder [37]. Nevertheless,
our Raman spectrum of b-Na4Cu(MoO4)3 can be clearly separated
into two regions with a wide empty gap in the 500-700 cm1 range
that is characteristic for molybdates containing MoO4 tetrahedra
[20,38]. Closer inspection of the Raman spectrum shows presence
of many bands above 750 cm1 that correspond to the MoO4
stretching modes. This observation is consistent with the mono-
clinic symmetry of b-Na4Cu(MoO4)3 and presence of two crystal-
lographically unique MoO4 units located at low symmetry sites.
This feature is less clear in the IR spectrum since bands are not so
well resolved due to their large bandwidths. The n2 and n4 bending
modes are located in the 460-310 cm1 range. It can be noticed that
Raman bands corresponding to the n2 modes are much broader Fig. 5. Infrared and Raman spectra of b-Na4Cu(MoO4)3.
than the corresponding bands observed in the MoO4 stretching
region. This behavior suggests that translations of the disordered
copper and sodium ions also contribute to these modes to some Table 7
Assignment of the internal vibrational modes of MoO4 tetrahedra.
extent. However, based on reported vibrational studies of other
molybdates and tungstates containing sodium and copper ions Assignment Infrared (n/cm1) Raman (n/cm1)
[39e41], we conclude that translational motions of Naþ, Cu2þ and n1(MoO4) 913 938, 925, 903, 896, 885
MoO2 2
4 ions as well as librational modes of MoO4 ions contribute n2(MoO4) 338, 311
most strongly to the modes observed below 250 cm1. n3(MoO4) 860, 828, 784 872, 856, 842, 831, 816, 809, 787, 751
n4(MoO4) 467 458, 432
3.4. Optical studies

a/S, such that a/S ¼ F(Rd) ¼ (1-R)2/2R, where a and S are the ab-
In order to determine the value of band gap energy (Eg) for b-
sorption and scattering coefficients, respectively [42,43]. The band
Na4Cu(MoO4)3, we employed the Kubelka-Munk theory. This
gap energy determined from the diffuse reflectance spectrum is
method makes it possible to connect the reflectance Rd by the term
Fig. 6. Diffuse reflection spectrum of b-Na4Cu(MoO4)3.
equal to 2.15 eV (Fig. 6). For the determination of band gap nature
(direct or indirect gap), the optical gap value is estimated relying on
the KubelkaeMunk method integrated with the Tauc relation:
(ahn)g ¼ A(hn-Eg). In this relation, hn denotes the energy of the
photons, A is an energy-dependent constant and g is a constant that
assumes different values depending on the electronic transition
type, i.e., g ¼ 1/2 for an indirect transition and g ¼ 2 for a direct
transition [44]. By plotting (F(Rd)hn)2 as a function of the excitation
energy, we have estimated the direct band gap energy. Similarly,
energy of the indirect band gap was estimated by plotting (F(Rd)
hn)1/2 as a function of the excitation energy. The calculated values
of direct and indirect band gap derived from the KubelkaeMunk
method combined with the Tauc relation are 1.76 and 3.00 eV,
respectively (Fig. 7). The data collected in reflectance mode are
manually converted into absorbance units (u.a) by the relation A ¼ -
log(Rd) [45]. The absorbance spectrum of b-Na4Cu(MoO4)3 contains
a wide and intense low energy absorption band, centred at 1.38 eV
(Fig. 8). This band can be attributed to the laporte-forbidden d-
Fig. 7. (a) Direct and (b) indirect bang gap of b-Na4Cu(MoO4)3.
d transition 2Eg / 2T2g of Cu2þ located in distorted octahedral
(4 þ 2) coordination [46]. The second absorption band at high
energy extending from 2.15 to 4.13 eV corresponds to the O(p)-
Cu(d) ligand to metal charge transfer transition (LMCT) [47]. The
band gap energy determined from the intersection of the tangent to
the absorbance curve and the horizontal axis is equal to 2.17 eV. The
obtained values of the band gap derived using different methods
indicate that b-Na4Cu(MoO4)3 has a semiconductor nature. We note
that the energy value in the case of the indirect gap (in the case
where g ¼ ½) is very close to those determined by the diffuse
reflectance method and from the absorption curve. Therefore, this
compound appears to have an indirect band gap.
4. Conclusions
The performed studies revealed that grain boundaries cause a

partial blockage of the carriers charge, which reduces the total
conductivity of the materiel. This blockage can be quantitatively
characterized by the blocking factor a and is inversely proportional
to the temperature. Based on the results of complex impedance
study, it can be concluded that b-Na4Cu(MoO4)3 can be used in
energy storage provided that we minimize the effect of grain
boundaries. This requires further study of its microstructure. The Fig. 8. Electronic absorption spectrum of b-Na4Cu(MoO4)3.
infrared and Raman studies allowed us to propose assignment of [19] R.L. Frost, J. Bouzaid, I.S. Butler, Raman spectroscopic study of the molybdate
mineral szenicsite and comparison with other paragenetically related
vibrational modes to respective motions of atoms in the unit cell.
molybdate minerals, Spectrosc. Lett. 40 (2007) 603e614, https://doi.org/
They also demonstrated a good agreement between the factor 10.1080/00387010701301220.
group analysis and the experimental data. Optical studies showed [20] M. Maczka, A.G. Souza Filho, W. Paraguassu, P.T.C. Freire, J. Mendes Filho,
that b-Na4Cu(MoO4)3 is a semiconductor with indirect band gap. J. Hanuza, Pressure-induced structural phase transitions and amorphization in
selected molybdates and tungstates, Prog. Mater. Sci. 57 (2012) 1335e1381,
The existence of indirect band gap implies that electronic con- https://doi.org/10.1016/j.pmatsci.2012.01.001.
duction in this compound needs both photons and phonons [21] W. Dridi, M.F. Zid, Synthesis, crystal structure and charge-distribution vali-
energies. dation of b-Na4Cu(MoO4)3 adopting the alluadite structure-type, Acta Crys-
tallogr. E Crystallogr. Commun. 72 (2016) 1103e1107, https://doi.org/
10.1107/S2056989016010367.
Conflict of interest [22] K.M. Khal’baeva, S.F. Solodovnikov, E.G. Khaikina, Y.M. Kadyrova,
Z.A. Solodovnikova, O.M. Basovich, K.M. Khal’baeva, S.F. Solodovnikov,
E.G. Khaikina, Y.M. Kadyrova, Z.A. Solodovnikova, O.M. Basovich, Phase for-
The author(s) declare(s) that there is no conflict of interest mation in the Li2MoO4eRb2MoO4eFe2(MoO4)3 system and crystal structure of
regarding the publication of this paper. a novel triple molybdate LiRb2Fe(MoO4)3, J. Solid State Chem. 203 (2013)
227e231, https://doi.org/10.1016/j.jssc.2013.04.020.
[23] A.A. Savina, V.V. Atuchin, S.F. Solodovnikov, Z.A. Solodovnikova, A.S. Krylov,
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Journal of the Iranian Chemical Society
https://doi.org/10.1007/s13738-022-02715-4
ORIGINAL PAPER
Synthesis, crystal structure and alkaline pathways simulation

of K3Na(Mo0.67Cr0.33O4)2 adopting glaserite structure‑type
Wassim Dridi1 · Amira Marzouki2 · Youssef Ben Smida3 · Ameni Brahmia4,5 · Riadh Marzouki1,4,6 ·
Mohamed Faouzi Zid1
Received: 3 March 2022 / Accepted: 2 December 2022

© Iranian Chemical Society 2022
Abstract
A new compound, K3Na(Mo0.67Cr0.33O4)2, had been synthesized using the flux method and characterized by single-crystal
X-ray diffraction. The title compound could be considered as a new member of the Glaserite family. The crystal structure is
built on (Mo/Cr)O4 tetrahedra sharing corners with NaO6 octahedra making a 2D formwork. The Mo6+ and Cr6+ cations are
located at the same general site with occupancies of 0.67 and 0.37, respectively. The proposed structural model was supported
by the bond valence sum and the charge distribution validation methods with suitable agreement factors. The experimental
morphology of the single crystal determined by SEM technique and the simulated morphology from the crystallographic
data have been reported. The simulation of the alkaline elements pathways migration by using the bond valence site energy
model shows that the potassium atoms are blocked and only the sodium atoms can move. The estimated activation energy
is about 1.45 eV. The crystal structure and the isosurfaces of migration of alkaline cations in crystal structure of the title
compound and in the AIMIII(MoO4)2 (AI = alkaline; MIII = Fe3+, Cr3+, V3+, Al3+) compounds were compared.
Keywords Glaserite structure · Bond valence analysis · Charge distribution · BVSE model · Pathways simulation
Introduction
Molybdates constitute an important class of materials exhib-

iting great structural diversity. This diversity comes from the
ability of (MoO4)2− groups to associate with transition metal
* Youssef Ben Smida polyhedron to form 1D, 2D and 3D frameworks [1–11]. The
youssef.bensmida@fst.utm.tn physicochemical properties of molybdates are correlated
with the nature and the oxidation number of the cations as
1
Laboratory of Materials, Crystallochemistry and Applied well as to the crystal structure. Thus, the molybdate materi-
Thermodynamics, Faculty of Sciences of Tunis, University
of Tunis El Manar, 2092 El Manar II, Tunis, Tunisia als have been used in several applications in various fields
2 such as the solid-state electrochemistry [8–11].
Laboratory of Signal Image and Energy Mastery,
Engineering National Higher School of Tunis, Tunis, Tunisia The molybdates with glaserite-type [12–18] are well-
3 known class of materials. The material with formula
Laboratory of Valorization of Useful Materials, National
Center of Materials Sciences Research, University K3Na(SO4)2 was identified for the first time by Gossner
of Carthage, Technopole Borj Cedria, BP 73, 8027 Soliman, in 1904 [19], and later the structure was determined and
Tunisia confirmed several times [20–22]. Indeed, the materials with
4
Chemistry Department, College of Science, King Khalid glaserite-type structure have a general chemical formula
University, Abha 61413, Saudi Arabia as A3B(EX4)2 (A, B = Li, Na, K, Rb, Cs, NH4; EX4 = SO4,
5
Laboratoire des Matériaux et de l’Environnement pour le SeO4, CrO4, WO4, RuO4, BeF4, MoO4) and crystallize in
Développement Durable, LR18ES10, Université de Tunis different crystallographic systems ranging from trigonal,
El Manar, ISSBAT, 9, Avenue Dr. Zoheir Safi, 1068 Tunis, orthorhombic to monoclinic where the symmetry of the
Tunisia
structure depends on the size of the ions involved. The ideal
6
Chemistry Department, Faculty of Sciences of Sfax, glaserite-type structure is trigonal, space group P-3m [23].
University of Sfax, BP 1171, 3000 Sfax, Tunisia
13
Vol.:(0123456789)
However, most of glaserite-type compounds undergo a followed by fast cooling with a rate of 50 °C per hour to the
phase transition upon cooling into a low-temperature phase, room temperature. The excess of reagents is removed by
which generally has a lower symmetry than the ideal trigonal washing the crystals with hot water. The yield of this type of
structure [24]. In ideal glaserite-type structures, the cations reaction is low in terms of number and quantity of crystals,
occupy three different sites. The octahedral site at 0, 0, ½, but this method is effective in the obtaining of new materi-
(1b, -3m, one quarter of cations number) must be occupied als as single crystals and in the reduction of the synthesis
by the smallest cation. The largest cations occupy the site temperature.
located on the trigonal axis (1/3, 2/3, z, 2d, 3m, one half of
cations number, coordination 10) and the position at (0, 0, Energy‑dispersive X‑ray spectroscopy
0) coordination 12 (1a, -3m, one quarter of the ion) [18].
The molybdates materials could be synthesized as single The single-crystal morphology and EDX analysis have been
crystal with different methods [25] such as the solid-state carried out using a FEI QUANTA 200 scanning electron
method [1, 2, 4–6] and flux [26, 27]. Also, the molybdate microscope.
materials could be obtained as hybrid compounds organic
and inorganic [28–30]. The obtaining of the single crystal Morphology calculation
is the best way to explore new materials. When the crystal
structure of the new molybdates is resolved and refined; the The crystal morphology simulation has been done by using
polycrystalline powder could be prepared by several meth- the BFDH method by means of WinXMorph software [35].
ods [31]. On the other hand, the molybdates materials could
be used in several fields such as ionic conductivity [3, 8, 10, X‑ray single‑crystal diffraction
11], optic [8, 32, 33], magnetic [10].
In this context, this paper studies a new molybdate of A red crystal of 0.24 × 0.20 × 0.18 mm3 dimension was
transition elements. The new compound has been obtained selected for data collection under binocular magnifier and
by flux method, and the structure was resolved and refined polarizing microscope. The X-ray single-crystal diffrac-
from the data obtained from the X-ray single-crystal dif- tion has been done at room temperature by the main of
fraction. The crystal structure was confirmed by checkcif Enraf-Nonius CAD4 diffractometer using graphite mono-
routine and two validation methods. The particularity of chromatic Mo-Kα radiation (λ = 0.7107 Å) in the range of
the title compound was discussed, and the crystal structure 2.3° ≤ θ ≤ 27.0°. Six intense reflections with angle ψ > 120°
was compared to the other materials of the Glaserite family. were chosen for the empirical ψ-scan absorption correction.
Bond valence site energy method was adopted to simulate
the ionic motions in the anionic frameworks. Crystal structure validation models (CHARDI
and BVS)
Experimental section Besides the validation using the checkcif, two models of
validation of structures, widely employed, were used in
Synthesis this study: the bond valence sum (BVS) [36, 37] and the
charge distribution CHARDI [38, 39]. In brief, the BVS
In order to obtain K 3Na(Mo0.67Cr0.33O4)2, the following and CHARDI models calculate, respectively, the valence
reagents: Na2CO3 (0.5 g) (Fluka, 99.0%), K 2CO3 (0.435 g) V(i) and charge Q(i) of the atom (i) following two differ-
(Prolabo, 99.0%), ( NH4)6Cr2O7 (0.552 g) (Sigma-Aldrich, ent models. The total deviation of the valences and charges
99.9%) and ( NH4)6Mo7O24·4H2O (5 g) (Fluka, 99%) were calculated from the formal oxidation numbers is calculated
weighted in the proportions Na: K: Cr: Mo = 3: 2: 1: 6 and by using the global instability index GII for the BVS [40]
dissolved in 10 ml of an aqueous solution of nitric acid and the mean absolute percentage deviation of the cation
(9 M). The molybdate (NH4)6Mo7O24·4H2O was used in σcat and anion σani for CHARDI [39]. CHARDI allows to
excess, and it plays the role of flux which decreases the tem- quantify the distortion of the polyhedra by the calculation
perature of the reaction [34]. Then, the mixture was dried at of the effective coordination number ECoN. The results of
100 °C. The obtained powder was grounded and preheated BVS and CHARDI calculation are summarized in Table 4.
at 180 °C for 24 h. In this step, CO2, NH3 and H2O are
eliminated and only the oxides remain. The obtained powder Conduction pathways simulation method
was grounded and heated at 480 °C. The mixture was left
at this temperature for 1 week to promote the germination The bond valence site energy (BVSE) model has been used
and the growth of the crystals. Subsequently, the furnace to simulate the transport pathways of K+ and N
a+ in the
was slowly cooled with a rate of 5 degrees per day to 440 °C, structure. The BVSE model was used successfully in the
13
determination of the pathways of N a+ in N a4Co7(AsO4)7,

N a 2 CuP 1.5 As 0.5 O 7 and N a 2 CoP 1.5 As 0.5 O 7 [41–43],
and K + in K 3 Bi 6.5 (PO 4 ) 7.5 , K 0.405 Bi 0.865 AsO 4 and
Na2.77K1.52Fe2.57(AsO4)4 [44–46].
The BVSE model is the latest development of the theory
of the bond valence (BV) proposed by Pauling in 1929 to
explain the formation of same inorganic compounds [47].
This model was developed by Brown in several times [36,
37, 48, 49] and then by Stefan Adams [50, 51]. The BV
model has been used by Mazza [52] for the first time to
simulate the transport of N a+ in NaSICON compound. Then,
this model was transformed to band valence map which
allows a good visibility of the cations pathways in the struc-
tures [53, 54] using the valence unity (v.u) [55, 56] as an
arbitrary unity.
The last development of the BV model consists on the
conversion of the arbitrary unit (v.u) of valence to an energy
unit (eV) [57, 58]. This new model, called the BVSE (bond
valence site energy), allows to calculate the energy of every
site in the crystal structure by assimilating the anion–cation
bond to Mors’s type and the cation–cation to a Colombian
interaction. The total energy can be calculated by the fol-
lowing formula:
� �2
⎡� N sA−X − smin, A−Xi ⎤
E(A) = D0 ⎢ i
− N ⎥ + ECoulomb (A − B)
⎢ i=1 smin,, A−Xi ⎥
⎣ ⎦
(1)
where the ECoulomb term describes the electrostatic interac-
tions of the cation A with the framework. For more detail,
see references [57–59].
Results
Fig. 1 a EDS spectrum of K 3Na(Mo0.67Cr0.33O4)2 single-crystal, b
Morphology and EDX analysis experimental crystal morphology (SEM image) and c BFDH pre-
dicted morphology [morphological importance (MI) faces are shown
Before the X-ray single-crystal diffraction, we have checked together with their Miller indices]
the presence of the Na, K, Cr, Mo elements used in the syn-
thesis. The result of the EDX analysis is presented in Fig. 1
confirming the presence of the expected chemical elements. atoms (Cr and Mo) located at the same crystallographic site
The micrograph SEM and the simulated morphology are leads to well define the anisotropic agitation factor of cati-
slightly different (Fig. 1), and this may be explained by the ons. The oxygen atom O1 was split to two sites (O11 and
synthesis method which almost gives crystal with disfigured O12). The maximum and minimum electron densities in the
morphology. final Fourier difference map are acceptable and located at
− 0.79 eÅ−3 and 1.26 eÅ−3 near the oxygen atom O2. The
Crystal structure determination and validation intensity data were corrected for Lorentz and polarization
effects, and an empirical ψ-scan absorption correction was
The crystal structure was solved and refined in the P-3 applied.
space group using the direct methods and performed by the The crystallographic data, X-ray collection condition and
SHELXS97 program [60] included in the system WinGX refinement results are given in Table 1. The atomic coordi-
[61]. The first refinement cycles allow to locate most of the nates and equivalent isotropic displacement parameters are
atoms. The use of EADP and EXYZ constraints for the two listed in Table 2. Same selected interatomic distances (Å) are
13
Table 1 Crystallographic
data, collect conditions Crystallographic data
and refinement Results for Chemical formula K3Na(Mo0.67Cr0.33O4)2
K3Na(Mo0.67Cr0.33O4)2 CCDC number 2206113
Crystal form; crystal color; crystal size (mm3) Prism; Red; (0.22 × 0.16 × 0.12)
T (°C) 20
Crystal system; space group Trigonal; P-3
a (Å); c (Å); V (Å3); Z 5.097 (2); 7.5224 (9); 231.41 (4); 1
Dcal; μ (mm−1) 3.09; 4.00
Collect conditions
Diffractometer Enraf Nonius CAD4
θ range for data collection 2.7–26.9°
Limiting indices h = − 7 → 7; k = − 7 → 7; l = − 9 → 9
Scanning mode ω/2θ
Refinement results
Absorption correction; Tmin; Tmax Psi-Scan; 0.426; 0.528
Refinement method Full-matrix least-squares on F2
Agreement factors; Goof factor R(F2) = 0.034; wR(F2) = 0.084; S = 1.25
No. of reflections 2024
No. of independent reflections 344
Reflections used [I ≥ 2σ(I)] 337
Number of variable parameters 27
Minimal residual electronic density (e Å−3) − 0.79
Maximum residual electronic density (e Å−3) 1.26
Table 2 Atomic coordinates Atom X y z Wyck Ueq (Å2) Occ. (< 1)

and equivalent isotropic
displacement parameters (Å2) Mo1 2/3 1/3 0.27705(10) 2d 0.0228 (4) 0.67
Cr1 2/3 1/3 0.27705(10) 2d 0.0228 (4) 0.33
K1 2/3 1/3 0.8289 (3) 2d 0.0405 (6)
Na1 1 0 1 1a 0.0189 (8)
K2 1 0 1/2 1b 0.0675 (12)
O11 0.779(12) 0.627 (15) 0.174 (11) 6g 0.066 (4) 0.275 (9)
O12 0.835 (4) 0.646 (5) 0.206 (4) 6g 0.066 (4) 0.725 (9)
O2 2/3 1/3 0.4981 (15) 2d 0.071 (3)
regrouped in Table 3. The results of the BVS and CHARDI The coordination numbers CN for different cations seem
calculation are gathered in Table 4. high, and this is due to the splitting of the oxygen atom
O1 in two positions which allows to count the oxygen O1
twice. Normally, if the oxygen O1 completely occupies only
Crystal structure description one site, we have the Mo/Cr in a tetrahedron environment,
the sodium atom in an octahedron site, the potassium K1
The structural model was confirmed by the two models of being surrounded by 13 oxygen atoms and K2 by 12 oxygen
validation BVS and CHARDI. The M (Mo0.67Cr0.33) poly- atoms. Thus, in the crystal structure description, we will
hedron is slightly distorted with an effective coordination consider these environments to simplify the description and
number ECoN (M) = 6.98, and the arithmetic average dis- the figures.
tance dar is equal to the weighted average distance dmed. The The asymmetric unit of the title compound (Fig. 2)
potassium polyhedral is very distorted, and this is often is formed by two potassium atoms (K1 and K2) and one
observed for alkaline elements. The sodium atom is sur- sodium atoms (Na1) all in special positions (2d, 1b and
round by twelve oxygen atoms, and its polyhedron is slightly 1a, respectively). The chromium (Cr1) and molybdenum
distorted with ECoN (Na1) = 11.93. (Mo1) atoms occupied the same special position (2d). The
13
Table 3 Selected
interatomic distances (Å) for M—O2 1.66(1) K1—O12vii 2.92 (2) K1—O11v 2.79 (7) Na1—O11ix 2.34(7)
K3Na(Mo0.67Cr0.33O4)2 M—O12i 1.70(2) K1—O12viii 2.92 (2) K1—O11vi 3.19 (7) Na1—O11vi 2.34(7)
M—O12ii 1.70(2) K1—O11ix 3.01 (9) K1—O11vi 3.19 (7) Na1—O11xiv 2.34(7)
M—O12 1.70(2) K1—O11x 3.01 (9) K1—O12iii 3.06 (2) Na1—O12iii 2.40(2)
M—O11i 1.71(7) K1—O11xi 3.01 (9) K1—O12iv 3.06 (2) Na1—O12xii 2.40(2)
M—O11ii 1.71(7) K2—O12xv 2.87(3) K1—O12vi 2.92 (2) Na1—O12xiii 2.40(2)
M—O11 1.71(7) K2—O12vi 2.87(3) K1—O12v 3.06 (2) Na1—O12vi 2.40(2)
K1—O2 2.49 (1) K2—O12i 2.87(3) K1—O12v 3.07 (3) Na1—O12ix 2.40(2)
K1—O11iii 2.79 (7) K2—O12xiii 2.87(3) K1—O12v 3.07 (3) Na1—O12xiv 2.40(2)
K1—O11iv 2.79 (7) K2—O12xvi 2.87(3) Na1—O11iii 2.34(7)
K1—O11v 2.79 (7) K2—O12iii 2.87(3) Na1—O1xii 2.34(7)
K1—O12vi 2.92 (2) K2—O11vi 3.12(9) Na1—O11xiii 2.34(7)
Symmetry codes: (i) − x + y + 1, − x + 1, z; (ii) − y + 1, x − y, z; (iii) y, − x + y, − z + 1; (iv) x − y + 1, x, − z + 1;

(v) − x + 1, − y + 1, − z + 1; (vi) − x + 2, − y + 1, − z + 1; (vii) x − y, x − 1, − z + 1; (viii) y, − x + y + 1, − z + 1;
(ix) − x + y + 1, − x + 1, z + 1; (x) x, y, z + 1; (xi) − y + 1, x − y, z + 1; (xii) − y + 2, x − y, z + 1; (xiii) x − y + 1,
x − 1, − z + 1; (xiv) x, y − 1, z + 1; (xv) x, y − 1, z; (xvi) − y + 2, x − y, z
Table 4 CHARDI and BVS Cation q(i).sof(i) Q(i) V(i) CN(i) ECoN(i) dar dmed
analysis of cation polyhedra in
K3Na(Mo0.67Cr0.33O4)2 M 6.00 6.16 6.433 7 6.98 1.701 1.701
K1 1.00 0.94 1.046 19 15.63 3.010 2.912
K2 1.00 1.07 0.831 18 14.51 3.145 3.023
Na1 1.00 0.85 1.126 12 11.93 2.367 2.365
M = Mo0.67Cr0.33, q(i) = formal oxidation number, sof(i) = site occupation factor, Q(i) = calculated charges,
CN = coordination number, ECoN = number of effective coordination, dar = arithmetic average distance,
dmed = weighted average distance
Fig. 3 Representation of the coordination polyhedra of

K3Na(Mo0.67Cr0.33O4)2 in the ab plan showing the connection
Fig. 2 Asymmetric unit of the K3Na(Mo0.67Cr0.33O4)2 crystal showing between the octahedron and the tetrahedron
the environment of the Chromium and molybdenum atoms. (Symme-
try code: (i) 1 − x + y, 1 − x, z; (ii) 1 − y, x–y, z)
of a MO4 tetrahedron are shared with NaO6 octahedron,
whereas one oxygen atom is non-bridging. On the other
coordination is provided by two oxygen atoms where O1 hand, each Na atom is linked to six different MO4 octahe-
oxygen position is split in two general sites. drons to form layers with formula [Na(MO4)2]3− (Fig. 3)
The crystal structural of K 3 Na(Mo 0.67 Cr 0.33 O 4 ) 2 is parallel to the ab plan. The charge neutrality is assured
formed by NaO6 octahedron and MO4 (M = Cr/Mo) tet- by potassium cations which are located in the interlayer
rahedron connected by tops. Three of the oxygen atoms space (Fig. 4).
13
Table 5 Energy and atoms coordinate of equilibrium and interstitial

sites
Site Multiplicity x y z Energy (eV)
Na1 1 0.000 0.000 0.000 0.000

i1 6 0.708 0.847 0.385 1.153
i2 6 0.167 0.333 0.073 1.160
i3 3 0.000 0.500 0.000 1.272
i4 6 0.514 0.028 0.990 1.272
i5 2 0.000 0.000 0.688 1.286
Fig. 4 Representation of the coordination polyhedra of

K3Na(Mo0.67Cr0.33O4)2 in the bc plan showing the positions of potas-
sium atoms
Fig. 6 Projection of the unit cell showing the equilibrium site of

sodium (bleu balls) and interstitials sites (green balls).
from 2.87(3) Å to 3.12(9) Å, with an average distance of

2.95 Å. The Na–O distances range from 2.34(7) Å to 2.40(2)
Å (see Table 3 showing the main interatomic distances),
with an average distance of 2.37 Å (Table 4).
Fig. 5 K1 and K2 cations environments Alkaline conduction pathways simulation
The simulation of the transport pathways of N a+ and K

+ in
Figure 5 shows the environments of the two potassium the K3Na(Mo0.67Cr0.33O4)2 has been done by used the softBV
atoms. K1 has [3 + 3] coordination type. Indeed, K1 is software [59]. The results of the calculation are regrouped in
located between two layers and surround by three oxygen Tables 5 and 6. The BVSE calculation shows that the potas-
atoms from one layer and three others from the other layer sium ions are blocked in the anionic framework and can’t
(Fig. 5). The second potassium K2 is surrounded by ten participate in the cationic conduction (Fig. 7).
oxygen atoms and has [9 + 1] coordination type, one oxy- For the sodium ions, the BVSE calculation shows one
gen atom from a layer and nine others from the other layer equilibrium site and five interstitial sites, which have each
(Fig. 5). one site energy higher than 1 eV (Table 6). The BVSE model
The mean M–O distance (1.69 Å) in the MO4 tetrahe- also proposes eleven local pathways (Table 6). It is better to
dra (M = Cr, Mo) represents an average calculated from one visualize the equilibrium and interstitials sites in the unit
third of the distance CrVI–O [62] and two thirds of MoVI–O cell to link them. Figure 1 shows the sodium sites in the
[27]. The K1–O distances are in the range from 2.49(7) Å to unit cell. The interstitial sites are presented by green balls
3.19(7) Å, with an average distance of 2.99 Å. It is important (Fig. 6). The isosurfaces of Na+ migration in the structure
to note that some K–O distances are short (K1–O1 distance of K3Na(Mo0.67Cr0.33O4)2 are shown in Fig. 7.
is 2.49 (7) Å). Similar short distance was reported for the The investigation of the local migration pathways and
glaserite-type compounds [14]. The K2–O distances range the position of interstitial sites shows an infinity of possible
13
a+ in the K
Table 6 Local pathways of N 3Na(Mo0.67Cr0.33O4)2 this part, we will combine the crystallographic study and
Site 1 Saddle point Site 2 Energy (eV) Hope
the BVSE model to study the alkali migration in this type
distance materials with general formula: AM(MoO4)2 (AI = alkaline;
(Å) MIII = Fe3+, Cr3+, V3+, Al3+). Table 7 summarizes the crys-
tallographic system, space group and the calculated activa-
1 i2 s1 Na1 1.160 1.806
tion energy of some materials. Figure 8 regroups the projec-
2 i1 s2 i1 0.106 2.289
tion of same structure of the AM(MoO4)2 family.
3 i4 s4 i2 0.192 1.719
In general, the metal M III (Fe3+, Cr3+, V3+, Al3+) forms an
4 i2 s5 i3 0.192 1.806
octahedra which connects with the tetrahedra of Mo (Fig. 8)
5 i2 s6 i4 0.210 1.719
and the cations lodge in the tunnels, cavity and interlayer.
6 i4 s8 Na1 1.370 2.984
The octahedra and tetrahedra are connect by corner to form
7 i5 s9 i1 0.276 1.603
layers. The cations ions are located in the interlayer spaces.
8 i5 s10 i1 0.277 1.603
The structure is maintaining by Colombian interactions
9 i2 s11 i1 0.294 2.361
between layers and alkaline cations.
10 i5 s12 Na1 1.451 2.351
For the title compound, the chromium C r3+ was oxidized
11 i1 s13 i1 0.461 3.353 6+
to Cr and occupies the same site as Mo. The compound
was formed by isolated tetrahedra related to alkaline element
combinations to form an infinite pathway. The activation

energy of the sodium atoms is those of the superior saddle
points since the equilibrium site energy is zero. Therefore,
the sodium could move along the diagonals of the faces and
along the long diagonal. The potassium ions could block
this movement. The calculated activation energy is about
1.45 eV.
Discussion
The materials of A–M–X–O systems (A: alkaline, M = transi-

tion metal, X = P, Mo, As, V) are often used in the recharge-
able batteries. The static simulation methods such as the
BVSE or dynamic model (molecular dynamics) allow to
explain the certain experimental values of the conductiv- Fig. 7 Projection of the unit cell showing the isosurfaces of migration
ity or activation energy and could also predict them. In of Na+
Table 7 Crystallographic data Formula System S.G Ea (eV)* Ref.

of materials with formula
AIMIII(MoO4)2 (AI = alkaline; 1D 2D 3D
MIII = MIII = Fe3+, Cr3+, V3+,
Al3+) and calculated activation 1 LiCr(MoO4)2 Triclinic P-1 0.54 1.32 1.99 [11]
energy 2 CsV(MoO4)2 Hexagonal P-3m No pathways found [63]
3 CsFe(MoO4)2 Trigonal P-3 No pathways found [16]
4 RbFe(MoO4)2 Trigonal P-3 No pathways found [16]
5 LiFe(MoO4)2 Triclinic P-1 0.55 1.20 1.96 [64]
6 NaFe(MoO4)2 Monoclinic C2/c 0.80 1.06 – [65]
7 KFe(MoO4)2 Trigonal P-3c No pathways found [66]
8 K3Na(MoO4)2 Monoclinic C2/c 0.36** 0.36** 1.11** [14]
9 NaAl(MoO4)2 Monoclinic C2/c 0.93 0.93 – [67]
10 KAl(MoO4)2 Trigonal P-3m No pathways found [67]
11 LiAl(MoO4)2 Triclinic P-1 0.67 1.42 2.25 [68]
*
Calculated by using the BVSE model
**
Energy of Na migration
13
Fig. 8 Projection of the crystal structure of AIMIII(MoO4)2 family showing the type of connection between polyhedral
13
by Colombian interaction to form the crystal structure. The LiFe(MoO4)2, LiCr(MoO4)2 and LiAl(MoO4)2 materials
title compound K 3Na(Mo0.67Cr0.33O4)2 is isoformula with have close activation energy, and the isosurfaces (Fig. 9) are
the K3Na(MoO4)2 and K2.5Na1.5(MoO4)2 compounds [14]. similar. The little difference in the activation energy comes
However, the introduction of the chromium in the structure from the interaction metal-lithium and from the unit cell
allows to increase the symmetry from the monoclinic for parameters of the structure which are changed slightly by
K3Na(MoO4)2 to the trigonal for K 3Na(Mo0.67Cr0.33O4)2. changing the metal.
The transition from the trigonal to monoclinic was observed NaAl(MoO4)2 and NaFe(MoO4)2 have also close acti-
for K3Na(CrO4)2, K3Na(SO4)2 and K3Na(SeO4)2 which are vation energies for the 1D and 2D migrations (Table 7),
belong the glaserite type compounds, at low temperature and there is high similarity in the isosurfaces of migration
[69]. Thus, the introduction of Cr metal in the structure of (Fig. 8). NaK3(MoO4)2 has the lowest activation energy,
K3Na(MoO4)2 allows to stabilize the structure in the high and this may be explained by the absence of the interaction
symmetry space group. metal - sodium; also the sodium atoms occupied the corner
Form a structural point of view, the symmetry of the and the center of the faces which let it moves freely in the
structure of the AIMIII(MoO4)2 family depends enormously ab plan (Fig. 8).
on the alkaline element. Indeed, materials with Li or Na
cations exhibit low symmetry system (triclinic, monoclinic);
however, materials with K, Rb, Cs elements exhibit high Conclusions
symmetry system (trigonal, hexagonal). We can notice that
this remark is not available with the rare earth metals. In this work, a new compound with for mula
The alkaline migration pathways of the AM(MoO4)2 3Na(Mo0.67Cr0.33O4)2 has been synthesized by flux method
K
materials have been simulation, and the activation energy and its structure was determined from X-ray single-crystal
has been estimated by the means of the BVSE model. diffraction. The chemical composition was confirmed by
The calculated activation energy for one-dimensional 1D, qualitative energy-dispersive X-ray spectroscopy. The title
bidimensional 2D and three-dimensional 3D migration is compound crystallizes in the trigonal symmetry, space group
regrouped in Table 7. P-3, and it adopts glaserite structure-type. The structure is
The BVSE calculation don’t found any migration path- characterized by cationic and anionic disorders. The struc-
ways for K, Cs and Rb elements, and this may be due to tural model is validated by bond valence sum and charge
the interlayer space, and the size of the tested alkaline ele- distribution methods. The BVSE simulation shows that
ments. For the Li and Na base compounds, the isosurfaces of only the sodium atoms can move in the structure with an
migration in the anionic formwork are regrouped in Fig. 9. activation energy of about 1.45 eV. The materials with
Fig. 9 Isosurfaces of alkaline

migration in structure from
AIMIII(MoO4)2
13
IMIII(MoO4)2
glaserite structure-type with general formula A crystal structure of binary molybdate CsFe (MoO4)2. Crystallogr.
I III 3+ 3+ 3+ 3+
(A = alkaline; M = Fe , Al , V , Cr ) show that the Rep. 55, 591–593 (2010)
14. J. Fábry, V. Petricek, P. Vanek, I. Cisarova, Phase transition in
structure depends on the nature of alkaline elements and K3Na (MoO4)2 and determination of the twinned structures of
only the sodium elements can move in this type of materials K3Na (MoO4)2 and K 2.5Na1.5 (MoO4)2 at room temperature. Acta
with an activation energy which depends on the nature of Crystallogr. Sect. B Struct. Sci. 53, 596–603 (1997)
transition elements and the crystal structure. 15. E.S. Zolotova, Z.A. Solodovnikova, V.N. Yudin, S.F. Solo-
dovnikov, E.G. Khaikina, O.M. Basovich, I.V. Korolkov, I.Y. Fila-
Acknowledgements The authors extend their appreciation to the tova, Phase relations in the Na2MoO4–Cs2MoO4 and Na2MoO4–
Deanship of Scientific Research at King Khalid University for fund- Cs2MoO4–ZnMoO4 systems, crystal structures of Cs3Na (MoO4)2
ing this work through research groups program under grant number and Cs3NaZn2 (MoO4)4. J. Solid State Chem. 233, 23–29 (2016)
R.G.P.2/175/43. The authors thank the Tunisian Ministry of Higher 16. T. Inami, Neutron powder diffraction experiments on the lay-
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the framework of the laboratory program contract (LR16CNRSM02). (SO4)2. J. Solid State Chem. 180, 2075–2079 (2007)
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Chemical Papers
https://doi.org/10.1007/s11696-020-01144-y
ORIGINAL PAPER
Vibrational and optical studies of Na0.45K1.55Cu3(MoO4)4

Wassim Dridi1 · Riadh Marzouki1,2,3 · Majed M. Alghamdi2 · Mahmoud A. Sayed4,5 · Miroslaw Maczka6 ·
Mohamed Faouzi Zid1 · Maciej Ptak6
Received: 28 October 2019 / Accepted: 28 March 2020

© Institute of Chemistry, Slovak Academy of Sciences 2020
Abstract
Sodium potassium copper(II) tetra-[molybdate(VI)], Na0.45K1.55Cu3(MoO4)4, was synthesized using solid-state reaction route,
and its crystal structure (monoclinic P21/c) was solved using single-crystal X-ray diffraction method. N a0.45K1.55Cu3(MoO4)4
forms 3D framework with elongated cavities occupied by alkali ions. The factor group analysis of N a0.45K1.55Cu3(MoO4)4 was
applied for determination of number and activity of internal and external modes. Infrared and Raman vibrational spectra were
investigated, and assignment of observed IR and Raman modes was proposed. The three crystallographically independent
Cu2+ cations of N a0.45K1.55Cu3(MoO4)4 adopt the [4 + 2] C
uO6 Jahn–Teller distortion giving rise to an intense d–d transition
observed in UV–Vis absorption spectra. The energies of indirect (3.01 eV) and direct (2.17 eV) band gaps were calculated
using Kubelka–Munk method combined with the Tauc equation.
Keywords Molybdate · Phonon properties · Raman spectra · IR spectra · Band gap
Introduction spaces, tunnels or cages. The type of adopted structure deter-

mines the physicochemical properties of molybdates that
Molybdates form an important class of materials that exhibit from decades constantly attract a great attention due to their
a great structural variety. This feature originates from the potential applications in many fields.
ability of the MoO42− molybdate group to create different Research on molybdates is currently oriented toward
types of complex arrangements in solid state. The properties ionic conductivity (Khobrakova et al. 2008; Michael Chance
of molybdate-based networks are directly correlated with the and Zur Loye 2013), electronic and photonic technologies
formation of spaces that are able to accommodate different (Atuchin et al. 2015). Molybdates are also used in potential
types of metal counter-ions. The tetrahedral M oO42− ions application such as laser, luminescent hosts, light-emitting
can form coordination polymers with varied mixed struc- diodes (Kaczmarek and Van Deun, 2013) and cryother-
tures, which most often comprise cavities, i.e., interlayer mometers (Ahmed et al. 2018). The interpretation of laser
1
* Wassim Dridi Laboratory of Materials, Crystal Chemistry and Applied
wassimdridi35@yahoo.fr Thermodynamics, LR15ES01, Faculty of Sciences of Tunis,
University of Tunis El Manar, 2092 Tunis, Tunisia
Riadh Marzouki
2
riadh.marzouki@hotmail.fr Chemistry Department, College of Science, King Khalid
University, Abha 61413, Saudi Arabia
Majed M. Alghamdi
3
mmalghamdi@kku.edu.sa Chemistry Department, Faculty of Sciences of Sfax,
University of Sfax, 3038 Sfax, Tunisia
Mahmoud A. Sayed
4
wassimdridi35@yahoo.fr Physics Department, College of Science, King Khalid
University, Abha 61413, Saudi Arabia
Miroslaw Maczka
5
m.maczka@int.pan.wroc.pl Physics Department, Faculty of Science, Al-Azher
University, Asyût, Egypt
Mohamed Faouzi Zid
6
faouzi_zid@yahoo.fr Institute of Low Temperature and Structure Research, Polish
Academy of Sciences, P.O. Box 1410, 50‑950 Wrocław 2,
Maciej Ptak
Poland
m.ptak@int.pan.wroc.pl
13
Vol.:(0123456789)
Chemical Papers
properties requires the knowledge of vibrational level distri- temperature using a PANalytical X’Pert PRO X-ray diffrac-
bution (Hanuza and Macalik 1982); therefore, detailed pho- tometer equipped with copper anticathode (λ = 1.5406 Å).
non properties of molybdates also attract significant atten-
tion of scientific community (Saleem et al. 1983; Bazarov
et al. 2006; Isaac et al. 1997; Maczka et al. 2009; Hermano-
Results and discussion
wicz 2004; Kozhevnikova 2012; Frost et al. 2007). Molyb-
dates have also found applications as efficient and very
Crystal structure
active catalysts in oxidation of hydrocarbons (Pless et al.
2004; Saleem 1987; Ueda et al. 1997; Yoon et al. 1996).
It was previously shown based on the single-crystal meas-
It was previously shown that the ceramic materials with
urements that the Na0.45K1.55Cu3(MoO4)4 crystal adopts
the presence of the Cu–O bonds can cause high-temperature
the monoclinic P2 1/c symmetry and unit cell param-
superconductivity (Hanuza et al. 1990). Therefore, we have
eters a = 5.097(2) Å, b = 14.594(3) Å, c = 19.905(3) Å,
decided to study molybdates containing the A–Cu–Mo–O
β = 94.00(2)°, Z = 4 (Dridi and Zid 2018). The three-dimen-
(A = monovalent ion) systems. We showed in our previous
sional framework is composed of distorted [4 + 2] CuO6
paper that conductivity in N a0.45K1.55Cu3(MoO4)4 molybdate
octahedra and MoO4 tetrahedra form large elongated cavi-
obtained from the melt is limited by the grain boundaries
ties occupied by the N a+ and K
+ cations. The K2 and Na1
(Dridi and Zid 2018).
alkali ions are situated on the same general site with 0.55
Herein, we report synthesis of polycrystalline
and 0.45 occupancies, respectively (Dridi and Zid 2018).
Na0.45K1.55Cu3(MoO4)4 powder obtained by a solid-state
Figure 1a shows experimental XRD powder pattern com-
reaction method and spectroscopic analysis. We report
pared to the simulated one based on the previous single-
optical properties of N a0.45K1.55Cu3(MoO4)4 sample using
crystal refinement. It shows the crystalline character of syn-
UV–Vis-NIR diffuse reflectance spectroscopy as well as
thesized powder and that all reflections have close positions
phonon properties using Raman and IR spectroscopies. We
proving that the obtained Na0.45K1.55Cu3(MoO4)4 powder
also present IR and Raman selection rules and assignment
adopts the same P21/c symmetry and is free of impurities.
of observed bands based on factor group analysis.
The unit cell parameters refined from experimental XRD
pattern were calculated using a Celref 3.0 program as fol-
lows: a = 5.098(1) Å, b = 14.591(4) Å, c = 19.908(6) Å and
Materials and methods β = 94.01(2)°.
Synthesis of Na0.45K1.55Cu3(MoO4)4
Raman and IR studies
The Na0.45K1.55Cu3(MoO4)4 polycrystalline powder was
prepared by a solid-state reaction method using high- For the P21/c (C52h) structure of N
a0.45K1.55Cu3(MoO4)4, the
purity commercial reagents of Na2CO3 (Fluka, 99.0%), primitive cell contains 25 × 4 = 100 atoms occupying the 4e
K2CO3 (Fluka, 99.0%), Cu(NO 3)23H2O (Merck, 99.0%) (C1) positions generating the Γ4e = 3A(R) (R)
g + 3Bg + 3Au
(IR)
+3
(IR)
and (NH4)6Mo7O24·4H2O (Fluka, pa). The stoichiometric Bu irreducible representations. All 100 atoms of the primi-
amounts of precursors were mixed and heated progressively tive unit cell give rise to 300 Brillouin zone-center degrees
to 853 K in porcelain crucible. An intermittent cooling and of freedom predicted by group theory (Fateley et al. 1972)
regrinding were done for higher reactivity. that can be described by the full irreducible representation,
Γ = 75Ag(R) + 75Bg(R) + 75Au(IR) + 75B(IR)
u , further subdivided
Characterization into 3 acoustic (Γa = Au(IR) + 2Bu(IR)) and 297 optical (Γo =
75A(R) (R) (IR) (IR)
g + 75Bg + 74Au + 73Bu ) modes. The Au and B u
Mid-IR spectrum in the 400–4000 cm−1 range with 2 cm−1 modes are IR-active, and the Ag and Bg modes are exclu-
resolution was recorded at room temperature using a Thermo sively Raman-active; therefore, based on the group theory
Scientific Nicolet iS50 FT-IR spectrometer and standard Raman spectra are expected to contain 150 (Eq. 1) bands,
KBr method. The room-temperature Raman spectrum in the while IR spectra 147 (Eq. 2) bands:
100–1000 cm−1 range was recorded using LAB RAMAN
𝛤R = 75A(R) + 75B(R) ; (1)
HR800 spectrometer with 632.81 nm excitation and 2 cm−1 g g
resolution. The laser power was set to 1 mW to avoid sample

degradation and heating. The diffuse reflectance spectrum 𝛤IR = 74A(IR) + 73B(IR) . (2)
u u
in the 300–1800 nm range was measured at room tempera-
ture using a PerkinElmer (lambda 900) UV–Vis–NIR spec- a0.45K1.55Cu3(MoO4)4
The centrosymmetric structure of N
trometer. The XRD powder pattern was measured at room compound requires measurement of both IR and Raman
13
Chemical Papers
Fig. 1 Experimental and

simulated XRD powder pat-
terns together with Miller
indices (a) and polycrystal-
line IR and Raman spectra of
Na0.45K1.55Cu3(MoO4)4 (b)
spectra to get an ultimate designation of the crystal at 365 cm−1 (Nakamoto, 1966). All of the above vibrational
modes (Hanuza, 1984). The correlation diagram for modes are Raman-active, while only F2-symmetry spe-
Na0.45K1.55Cu3(MoO4)4 compound based on the factor group cies, ν3 and ν4, are IR-active. If molybdate ion is placed
oO42− ion
analysis is presented in Table 1. The isolated M in the crystal frame, its symmetry is reduced as a result of
has ideal Td symmetry exhibiting four fundamental vibra- the lattice’s constraints. Therefore, the site symmetry of the
tions, i.e., ν1(A1) nondegenerate symmetric stretching at four MoO42− tetrahedra decreases to C1. In consequence,
936 cm−1, ν2(E) doubly degenerate symmetric bending at all vibrational modes transform into A-symmetry species;
220 cm−1, ν3(F2) triply degenerate asymmetric stretching at therefore, they become both IR- and Raman-active. Due to
895 cm−1 and ν4(F2) triply degenerate asymmetric bending the lack of degeneracy, the F-symmetry species (ν3, ν4) split
Table 1 Correlation table for N

a0.45K1.55Cu3(MoO4)4 structure
Ionic species (WP) Vibration Free ion symmetry Site symmetry Factor group symmetry
Td C1 C2h
MoO42− ν1 A(R)
1 A(R,IR) A(R) (R) (IR)
g + Bg + Au + Bu
(IR)
(4e) ν2 E(R) 2A(R,IR) 2Ag + 2Bg + 2Au + 2B(IR)

(R) (R) (IR)
u
ν3 F(R,IR)
2 3A(R,IR) 3A(R) (R) (IR)
g + 3Bg + 3Au + 3Bu
(IR)
ν4 F(R,IR)
2 3A(R,IR) 3Ag + 3Bg + 3Au + 3B(IR)
(R) (R) (IR)
u
T′ F(R)
1 3A(R,IR) 3A(R) (R) (IR)
g + 3Bg + 3Au + 3Bu
(IR)
L F(R,IR)
2 3A(R,IR) 3Ag + 3Bg + 3Au + 3B(IR)
(R) (R) (IR)
u
Ionic species (WP) Vibration Free ion symmetry Site symmetry Factor group symmetry
C1 C2h
Cu2+ (4e) T′ 3A(R,IR) 3A(R) (R) (IR) (IR)

g + 3Bg + 3Au + 3Bu
K1+ (4e) T′ 3A(R,IR) 3Ag + 3Bg + 3Au + 3B(IR)
(R) (R) (IR)
u
K2+/Na1+ (4e) T′ 3A(R,IR) 3A(R) (R) (IR) (IR)
g + 3Bg + 3Au + 3Bu
WP Wyckoff position, R Raman-active, IR IR-active, T′ translational, L librational mode
13
Chemical Papers
into 3A modes and E-symmetry mode (ν2) to 2 components bond (1.7146 Å) is equal to 941 cm−1 and agrees well with
(2A). the experimental wavenumber and is within the error limits.
It is well known that all observed vibrational modes can According to Brown and Wu, the Pauling bond strength in
be divided into two groups, external (lattice) and internal valence units (± 0.1) can be expressed as (Brown and Wu,
modes (Basiev et al. 1999). The internal modes of each 1976) (Eq. 6):
MoO42− ion can be subdivided into A(R) (R)
g + Bg + Au
(IR)
+ B(IR)
u
symmetric stretching (ν1), 2Ag + 2Bg + 2Au + 2Bu(IR
(R) (R) (IR) SMo−O = (R∕1.882)−6 (6)
)
symmetric bending (ν 2), 3Ag(R) + 3Bg(R) + 3Au(IR) + 3Bu(IR
) and for the shortest Mo–O length is equal to 1.75 vu, which
antisymmetric stretching (ν3) and 3Ag(R) + 3Bg(R) + 3A(IR)u corresponds to nearly double bond (Mo=O). The longest one
+ 3B(IR) antisymmetric bending (ν4) modes. The external
u corresponds to 0.96 vu, which is close to the single Mo–O
modes of M oO42− ion are divided into translational (T′) and
bond.
librational (L) modes (Nalbandian and Papatheodorou 1992),
The IR spectrum do not show such clear gap since IR
presented as follows (Eqs. 3, 4):
bands are broader compared to Raman and strongly over-
𝛤T� = 3A(R) + 3B(R) + 3A(IR) + 3B(IR) lapped. Based on the literature data (Baran et al. 1993), we
; (3)
assigned Raman bands in the 904–967 cm−1 region and IR
g g u u
band at 933 cm−1 to the symmetric stretching vibrations

𝛤L = 3A(R)
g
+ 3B(R)
g
+ 3A(IR)
u
+ 3B(IR)
u
. (4) of MoO42− originating from the ν1 vibration (see Tab. 2).
The antisymmetric components (based on the ν3 molecu-
Table 1 shows that the total number of modes for each lar vibration) were ascribed to Raman and IR bands in the
MoO42− ion in P21/c (C2h 5
) symmetry increases to 60, includ- 786–885 cm−1 and 780–885 cm−1 regions, respectively. The
ing 9Ag + 9Bg + 9Au(IR) + 9Bu(IR) internal, 3Ag(R) + 3Bg(R)
(R) (R)
Raman bands associated with symmetric and antisymmetric
+ 3A(IR)u + 3Bu
(IR)
translational and 3A(R) (R)
g + 3Bg + 3Au + 3
(IR)
bending modes of M oO42− tetrahedra, corresponding to ν4
(IR)
Bu librational modes. and ν2, are located in the 349–416 cm−1 and 257–330 cm−1
Figure 1b presents IR and Raman spectra measured for ranges, respectively. Raman bands observed below 232 cm−1
Na0.45K1.55Cu3(MoO4)4 molybdate. As one can see, strong were assigned to lattice modes, including translations and
Raman contours correspond to weak IR bands and vice oO42− groups as well as translations of
librations of the M
versa. The comparison of Raman and IR bands positions + + 2+
Na , K and Cu metal ions.
shows that observed bands do not coincide as expected
due to the presence of inversion center (centrosymmetric Optical studies
structure), i.e., the highest ν1 Raman band at 967 cm−1 cor-
responds to IR band at 933 cm−1 and ν3 bands at 885 and The diffuse reflectance UV–Vis spectrum is presented in
802 cm−1 are observed in IR spectrum at 867 and 780 cm−1 Fig. 2a. The broad high energy absorption band extending
(Kaoua et al. 2013; Junaid Bushiri et al. 2013). Moreover, from 300 nm (4.12 eV) to 560 nm (2.21 eV) corresponds
Fig. 1b also shows that Raman bands are observed in two to the (O–Cu) ligand-to-metal charge transfer of the CuO6
well-separated spectral regions with an empty gap in the group (Adler et al. 1990). It can be clearly seen that this
425–750 cm−1 range isolating stretching and bending vibra- contour is composed at least of two bands with the lowest
tions. This is commonly observed feature for molybdates energy matrix-related component with maximum at about
(Atuchin et al. 2014; Dridi et al. 2017a, b; Savina et al. 405 nm (3.06 eV). Second wide and intense absorption
2015). The Raman spectrum shows many bands above band, centered at about 968 nm (1.28 eV), corresponds to
750 cm−1 (in the Mo–O stretching region) which is in a the Laporte-forbidden 2Eg → 2T2g d–d transition of Cu2+
good agreement with the low symmetry (P21/c) monoclinic ions in distorted octahedral coordination (Ulutagay-Kartin
phase of N a0.45K1.55Cu3(MoO4)4 composed of four crystallo- et al. 2003). The band gap energy ( Eg) determined directly
graphically independent M oO42− tetrahedra. It is well known
that the wavenumber (ν) of Mo–O stretching vibrations cor-
relates (± 25 cm−1) with the bond length (R) by empirical
relation (Hardcastle and Wachs, 1991) (Eq. 5): Table 2 Assignment of the internal vibrational modes (cm−1) of
MoO42− tetrahedron
𝜈 = 32895 exp (−2.073R). (5) Assignment Infrared (ν/cm−1) Raman (ν/cm−1)
The highest obser ved Raman band for ν1 (MoO4) 933 967, 960, 955, 937, 925, 904
N a 0.45 K 1.55 Cu 3 (MoO 4 ) 4 molybdate corresponding to ν2 (MoO4) 330, 313, 277, 257
stretching vibration of shorter and terminal Mo–O bonds is ν3 (MoO4) 895, 867, 822, 780 885, 874, 840, 802, 786
observed at 967 cm−1. The calculated value for the shortest ν4 (MoO4) 416, 387, 371, 349
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Fig. 2 Absorption (a)

and F(R) (b) spectra of
Na0.45K1.55Cu3(MoO4)4 together
with (F(R)hν)1/2 (c) and
(F(R)hν)2 (d) Kubelka–Munk
graphical representations
from the absorption curve for the highest energy band was method. Therefore, this material appears to have an indi-
estimated to about 2.29 eV and is slightly lower in com- rect band gap. Band gap energy of Na0.45K1.55Cu3(MoO4)4
parison with determined using Kubelka–Munk theory and is located in the visible region, which is important for the
spectrum recalculated into F(R) according to Eq. 7 (2.32 eV, applications based on photocatalysis using solar energy
Fig. 2b) (Kubelka and Munk 1931; Samet et al. 2013; Sim- (Moura et al.2007).
mons 1975):
(1 − R)2 Conclusions
F(R) = , (7)
2R
where R denotes the reflectance. To determine the nature We have performed XRD and phonon (IR and Raman)
of band gap, Eg was estimated relying on the Tauc equation studies of polycrystalline Jahn–Teller distorted metal-
(Eq. 8): mixed Na 0 . 45 K 1 . 55 Cu 3 (MoO 4 ) 4 compound synthesized
using solid-state reaction method. The refinement of the
)n
(8) powder XRD pattern showed that it adopts monoclinic
(
(𝛼h𝜈) = k h − Eg ,
P2 1/c symmetry as previously reported for single-crys-
where k is an energy-dependent constant, hν is the photon tal experiment. Raman and infrared spectra confirmed
incident energy, and n is a constant that can take different the centrosymmetric character of the studied crystal and
values depending on electronic transition type, n = 1/2 for the low symmetry sites of molybdate ions arranged in
direct transition and n = 2 for indirect one (Murphy, 2007; deformed tetrahedral units giving rise to the many bands
López and Gómez 2012). The direct and indirect optical corresponding to stretching Mo–O vibrations. The calcu-
band gap energies were determined by extrapolating the lin- lated Pauling bond strengths for the Mo–O bonds revealed
ear fit of the plots of (F(R)hν)1/2 and (F(R)hν)2 as a function that they have character of single to nearly double bonds.
of the excitation energy (for the highest band only), respec- The number of expected modes has been calculated using
tively (Fig. 2c, d). factor group analysis and the tentative assignment of other
The calculated values of band gaps derived from the characteristic molecular vibrations of the M oO42− tetra-
Kubelka–Munk combined with the Tauc equation are hedra to the observed Raman and IR bands has been pro-
2.17 eV for direct gap and 3.01 eV for the indirect one. The posed. We also presented absorption spectrum of the stud-
obtained values indicate that N a0.45K1.55Cu3(MoO4)4 has a ied compound that was measured for determination of the
semiconductor behavior. We notice that the energy value direct (2.17 eV) and indirect (3.01 eV) band gap energies
in the case of the indirect gap is very near to those deter- using the Kubelka–Munk relation combined with the Tauc
mined by the absorption curve and from the Kubelka–Munk equation. The existence of indirect band gap implies that
13
Chemical Papers
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https://doi.org/10.1016/0022-2860(84)87189-6
Hanuza J, Macalik L (1982) Polarized i.r. and Raman spec-
Acknowledgements We would like to show our gratitude to the Dean- tra of orthorhombic KLn(MoO 4 ) 2 crystals (Ln = Y, Dy,
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Hindawi
Advances in Materials Science and Engineering
Volume 2017, Article ID 6123628, 8 pages
https://doi.org/10.1155/2017/6123628
Research Article
Electrical and Vibrational Studies of Na2K2Cu(MoO4)3
Wassim Dridi,1 Mohamed Faouzi Zid,1 and Miroslaw Maczka2

1
Laboratory of Materials, Crystal Chemistry and Applied Thermodynamics, Faculty of Sciences of Tunis,
University of Tunis El Manar, El Manar II, 2092 Tunis, Tunisia
2
Institute of Low Temperature and Structure Research, Polish Academy of Sciences, P.O. Box 1410, 50-950 Wrocław 2, Poland
Correspondence should be addressed to Mohamed Faouzi Zid; faouzi.zid@fst.rnu.tn
Received 1 December 2016; Revised 6 March 2017; Accepted 27 March 2017; Published 11 June 2017
Academic Editor: Pascal Roussel
Copyright © 2017 Wassim Dridi et al. This is an open access article distributed under the Creative Commons Attribution License,
which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.
The complex impedance of Na2 K2 Cu(MoO4 )3 material has been investigated in the temperature range of 653–753 K and in the
frequency range of 40 Hz–5 MHz. Electrical behavior of the studied material is explained through an equivalent circuit model which
takes into account the contributions of grains and grains boundaries. The number of vibrational modes was calculated using group
theoretical approach. The infrared and Raman spectra have also been measured and vibrational assignment has been proposed.
1. Introduction the copper molybdate Cu3 Mo2 O9 doped with lithium, which
displays high coulombic efficiency in lithium-ion batteries
A great deal of interest has been devoted to the chemistry and excellent charge-discharge stability [9]. Another example
of molybdenum; a significant number of new molybdates is Li2 Cu2 (MoO4 )3 material, which presents a high ionic
have been synthesized and characterized. Molybdate chem-
conductivity (𝜎 = 5.810−3 Ohm−1 ⋅cm−1 at 400 K, 𝐸𝑎 = 0.33 eV)
istry has developed rapidly and this development can be
[10].
explained by several factors, especially the improvement of
the structural X-ray diffraction analysis, which has been a The vibrational spectroscopic studies of molybdates
fundamental tool used for determination of crystal struc- have attracted particular attention of a large number of
tures. But this renewed interest is also explained by the fact researchers [11–16]. This attention is due to the catalytic
that many molybdates are suitable materials for technological activity of (MoO4 2− ) groups in hydrocarbons oxidations [17–
applications. Molybdates exhibit various physicochemical 20] and due to negative thermal expansion, ferroelasticity,
properties, which are related to both the nature of the ele- and pressure-induced amorphization [21]. Furthermore, the
ments associated with the molybdate groups and the degree interpretation of laser properties needs knowledge of vibra-
of opening of the formed framework. In these materials, the tional level distribution [22]. According to this approach,
anionic framework is usually built from MoO4 tetrahedra we have decided to explore system A-Mo-Cu-O (A = alkali
linked to the transition metal polyhedra, leading to a large metal). The purpose of this study is to analyze the elec-
variety of crystal structures with a high capacity for cationic trical response of the grain and grains boundaries effects,
substitution. The chemistry of inorganic molybdate materials which greatly influence the electrical properties, and to
has been significantly advanced thanks to their valuable understand the molecular structure at microscopic level of
electrical and optical properties, which make them promising novel Na2 K2 Cu(MoO4 )3 compound. This study can provide
for various applications such as photoluminescence [1], ionic important information on the conductivity, which is very
conductivity [2–4], laser materials [5, 6], and piezoelectrics important for practical applications. In this paper, we will
[7]. The high-temperature superconductivity present in the describe the synthesis method and the characterization
copper-oxygen ceramic systems resulted in an increasing of Na2 K2 Cu(MoO4 )3 by Infrared, Raman, and complex
structural and physicochemistry interest of materials con- impedance spectroscopies. Raman and IR selection rules will
taining Cu-O [8]. Among these materials we can mention be also analyzed using factor group analysis.
2 Advances in Materials Science and Engineering
5000 carried out after temperature stabilization of the device every

30 min with a pitch of 10 K. The advantage of this method
lies in the fact that it is possible to separate the physical
4000 phenomena according to their speed; the fast phenomena
will take place at high frequencies and the slow ones at low
frequencies. Analysis of impedance spectroscopy data can
3000 provide information on charge carrier dynamics in ionic
Intensity
conductors [23].
2000 2.3. Vibrational Spectroscopies. The infrared spectrum was
recorded at room temperature using Thermo Scientific Nico-
let iS50 FT-IR Spectrometer. The frequency range was from
1000 400 to 4000 cm−1 and the spectral resolution was 3 cm−1 . We
are interested only in the domain 400–1100 cm−1 containing
the most significant solid-state absorption bands. To obtain
0
the Raman spectrum of the powdered sample, LAB RAMAN
HR800 spectrometer was used. The frequency range was from
10 20 30 40 50 60 70 100 to 1100 cm−1 and the spectral resolution was 2 cm−1 . The
2휃∘ measurement was carried out on a thin pellet. The sample
Calculated was analyzed with an excitation wavelength of 632.81 nm
Experimental and a power was adjusted to 1 mW in order to avoid any
degradation. Spectroscopic studies are used to obtain the
Figure 1: Calculated and experimental powder X-ray diffraction distribution of vibrational levels and assignment to the
patterns of Na2 K2 Cu(MoO4 )3 . respective normal modes of Na2 K2 Cu(MoO4 )3 .
3. Results and Discussion

2. Experimental 3.1. Structure Description. Na2 K2 Cu(MoO4 )3 crystallizes in
the triclinic space group P-1 with 𝑎 = 7.4946(8) Å, 𝑏 =
2.1. Polycrystalline Powder Synthesis of Na2 K2 Cu(MoO4 )3 . 9.3428(9) Å, 𝑐 = 9.3619(9) Å, 𝛼 = 92.591(7)∘ , 𝛽 = 105.247(9)∘ ,
The Na2 K2 Cu(MoO4 )3 polycrystalline powder was prepared 𝛾 = 105.496(9)∘ , 𝑉 = 604.7(Å3 ), 𝑍 = 2, 𝑅(𝐹2 ) = 0.022,
by a conventional solid-state reaction from high-purity
and 𝑅𝑤 (𝐹2 ) = 0.056. Both cations K1 and K3 are located
starting reagents of Na2 CO3 , K2 CO3 , Cu(CO2 CH3 )⋅H2 O,
in the center of inversion, and all other atoms are at
and (NH4 )6 Mo7 O24 ⋅4H2 O. These reagents were weighted
general positions. The structure of Na2 K2 Cu(MoO4 )3 can
according to the stoichiometric ratio. They were mixed
be described as a one-dimensional framework formed by
and ground together in an agate mortar and heated pro-
ribbons arranged in parallel to a axis with interribbons
gressively to 773 K in porcelain crucible with intermittent
spaces containing Na+ and K+ monovalent cations directed
cooling and regrindings. The powder was analyzed by X-ray
to the free vertices of the tetrahedra MoO4 (Figure 2). These
powder diffraction, using a PAN-analytical X’Pert PRO X-
structural characteristics encouraged us to study the electrical
ray diffractometer equipped with copper anticathode (𝜆𝐾𝛼
properties. CIF file containing complete information on
= 1.5406 Å). The unit cell parameters were refined using
the studied structure was deposited with FIZ Karlsruhe,
Celref 3.0 program and calculated to be as follows: 𝑎 =
76344 Eggenstein-Leopoldshafen, Germany (fax: (+49)7247-
7.5010(7) Å, 𝑏 = 9.3411(4) Å, and 𝑐 = 9.3670(7) Å and 𝛼 =
808-666; e-mail: crysdata(at)fiz-karlsruhe(dot)de, deposition
92.59(3)∘ , 𝛽 = 105.32(9)∘ , and 𝛾 = 105.44(6)∘ . The powder X-
number CSD-430379).
ray diffraction pattern was in agreement with single-crystal
structure (Figure 1). 3.2. Electrical Properties. The Nyquist plots in the tempera-
ture range from 653 K to 753 K are shown in Figure 3. When
2.2. Complex Impedance Spectroscopy. Pellet was prepared by temperature increases, the radius of semicircles decreases
isostatic pressing at 4 kbar and sintering at 773 K for 12 h in and consequently the ionic conductivities increase with the
air with 10 Kmin−1 heating and cooling rates. The thickness temperature. We notice the presence of two hardly dis-
and surface of pellet were about 0.22 cm and 1.25 cm2 having a tinguishable semicircles, which proves the presence of two
geometric factor of 𝑒/𝑠 = 0.176 cm−1 . Electrical measurements relaxation phenomena. The first arc existing towards higher
were carried out in air by complex impedance spectroscopy frequencies corresponds to the movement of ions across
using Agilent 4294A Precision Impedance Analyzer in the the grain (bulk), which represents intrinsic conduction and
40 Hz–5 MHz frequency range and 653–753 K temperature gives rise to an intragranular resistance. The second arc,
range. The sinusoidal AC voltage applied is of 0.5 V. The observed at lower-frequency, corresponds to movement of
measuring cell having the sample inserted between two ions through the grain boundaries [24, 25]. The electrical
platinum discs used as ion-blocking electrodes is heated behavior of Na2 K2 Cu(MoO4 )3 is interpreted through an
in an electric oven under dry air. The measurements were equivalent electrical circuit formed by two cells arranged
Advances in Materials Science and Engineering 3
Mo K
Cu Na
Figure 2: Projection of Na2 K2 Cu(MoO4 )3 structure according to 𝑎 axis.
in series, constituted by the parallel combination of the In order to determine the direct conductivity for the grain
following: 𝑅g ‖ 𝐶1 and 𝑅gb ‖ CPE1 corresponding to the interior 𝜎g , grain boundary 𝜎gb , and total conductivity 𝜎tot , we
contributions of grains and grains boundaries, respectively. used the following equation:
𝑅g and 𝑅gb are the resistances of grains and grains bound- 𝑒 1
aries, respectively. 𝐶1 is the pure capacitance of grain and 𝜎𝑖 = ⋅ . (1)
𝑅𝑖 𝑠
CPE1 is the fractal capacitance constant phase element
according to grains boundary. Electrical parameters were Values of ionic conductivities in Na2 K2 Cu(MoO4 )3 material
measured as a function of temperature. The intercepts of are represented in Table 2.
the semicircular arcs with the real axis give an estimation The activation energies was obtained by linear fitting of
of the resistance of the studied material. Zview software the ionic conductivities values at different temperatures by
[26] was used to fit these curves. The total resistance, 𝑅total , applying the Arrhenius equation:
follows the relation 𝑅g + 𝑅gb = 𝑅total . The conformity 𝐸𝑎
between the experimental and calculated curves (fit) on the 𝑇 = 𝜎0 exp (− ), (2)
𝑘𝑏 𝑇
whole temperature range proves the validity of the proposed
equivalent circuit. Electrical parameters are represented in where 𝜎 is the temperature dependent ionic conductivity,
Table 1. 𝜎0 is the ionic conductivity at absolute zero temperature,
1.5 0.5
0.4
−Z㰀㰀 (105 Ohm)

1.0
0.3
0.2
0.5
0.1
0.0 0.0
0.0 0.5 1.0 1.5 2.0 2.5 3.0 0.0 0.2 0.4 0.6 0.8 1.0
Z㰀 (105 Ohm) Z㰀 (105 Ohm)
653 K 673 K 683 K 703 K
663 K Fit 693 K Fit
0.8
0.6
0.4
0.2
0.0
0.00 0.37 0.74 1.11 1.48 1.85
Z㰀 (104 Ohm)
713 K 743 K
723 K 753 K
733 K Fit
Figure 3: Complex impedance spectrum of Na2 K2 Cu(MoO4 )3 over temperature range 653 and 753 K.
Table 1: Simulated data of the electrical parameters for the proposed equivalent circuit.
𝑇 (K) 𝑅g (Ω) 𝐶g (F) 𝑅gb (Ω) 𝐶gb (F) ∑ 𝑅𝑖 (Ω)

653 2.087(4)105 1.118(2)10−11 2.874(1)106 8.683(2)10−11 3.083(1)106
663 1.354(1)105 1.078(1)10−11 1.877(2)106 9.442(1)10−11 2.012(2)106
673 9.711(9)104 9.131(4)10−11 1.339(2)106 9.908(4)10−11 1.436(2)106
683 6.797(9)104 9.639(5)10−12 9.159(1)105 1.032(1)10−10 9.838(9)105
693 4.915(3)104 9.010(1)10−12 6.499(8)105 1.078(3)10−10 6.991(3)105
703 2.913(9)104 7.893(2)10−12 3.610(6)105 1.145(4)10−10 3.901(9)105
713 1.283(3)104 6.905(2)10−12 1.677(1)105 1.349(2)10−10 1.805(3)105
723 8.670(1)103 6.781(3)10−12 9.794(8)104 1.518(1)10−10 1.066(1)105
733 6.670(2)103 6.793(4)10−12 6.197(5)104 1.578(2)10−10 6.864(5)104
743 4.831(3)103 7.066(1)10−12 3.464(6)104 1.803(2)10−10 3.947(7)104
753 2.715(2)103 7.954(2)10−12 1.377(1)104 1.984(2)10−10 1.648(6)104
𝐸𝑎 is the activation energy of cations migration, 𝑘𝑏 is the We note that the total conductivity of our compound
Boltzmann constant, and 𝑇 is the absolute temperature. The is less than the bulk conductivity but higher than the
variation of log(𝜎(S⋅K⋅cm−1 )) versus 1000/𝑇 (K−1 ) is repre- grain boundary one. This reveals the existence of a partial
sented in Figure 4. Activation energies values are represented blockage of the charge carriers by the grain boundaries [27].
in Table 3. Therefore, the conductivity of our material is limited by the
−2 0.95
0.94
−3
Ea = 2.02 eV 0.93
−4 0.92
0.91
−5
ln(휎 · T) (S·K·cm−1 )
Ea = 2.86 eV Ea = 1.55 eV 0.90

−6
0.89
훼
−7 0.88
Ea = 2.77 eV
0.87
−8
Ea = 1.63 eV 0.86
−9 0.85
Ea = 1.62 eV 0.84
−10
0.83
−11 0.82
1.30 1.35 1.40 1.45 1.50 1.55 1.60 650 660 670 680 690 700 710 720 730 740 750 760
1000/T (K−1 ) Temperature (K)
Grains Total Figure 5: Variation of the blockage factor 𝛼 with temperature.
Grain boundaries Fit
Figure 4: Arrhenius plot of conductivity of Na2 K2 Cu(MoO4 )3 .

Table 3: Activation energies in Na2 K2 Cu(MoO4 )3 material.
Table 2: Ionic conductivities measurements value as a function of Contribution Temperature range (K) 𝐸𝑎 (eV)
temperature in Na2 K2 Cu(MoO4 )3 material.
653–673 1.55
Grains
Conductivities (Ω cm−1 ) 673–753 2.02
𝑇 (K)
𝜎g 𝜎gb 𝜎total Grains boundaries
653–673 1.63
673–753 2.86
653 1.05310−6 7.65210−8 5.70710−8
653–673 1.62
663 1.62410−6 1.17210−7 8.74510−8 Total
673–753 2.77
673 2.26510−6 1.64210−7 1.22510−7
683 3.23610−6 2.40110−7 1.78810−7
693 4.47510−6 3.38410−7 2.51710−7
703 7.55010−6 6.09310−7 4.51010−7 3.3. Vibrational Study. Na2 K2 Cu(MoO4 )3 crystallizes in the
713 1.71410−5 1.31110−6 9.74810−7 triclinic space group P-1 which corresponds to 𝐶𝑖 factor
723 2.53710−5 2.24610−6 1.65010−6 group. There are two molecules per unit-cell, so there are
733 3.29810−5 3.54910−6 2.56310−6
also two molecules per Bravais cell. Mo1, Mo2, Mo3, Cu1,
K2, Na1, Na1, and O atoms occupy 𝐶1 symmetry whereas
743 4.55310−5 6.34910−6 4.45810−6
K1 and K3 atoms occupy 𝐶𝑖 symmetry. The Bravais cell
753 8.10310−5 1.59710−5 1.06710−5 comprises 40 atoms that have 120 zone center degrees of
freedom. The structure of Na2 K2 Cu(MoO4 )3 compound is
centrosymmetric; a complete assignment of the crystal modes
low conductivity of the grain boundaries. The influence of
requires both IR and Raman spectra [30]. The crystal vibra-
the grains boundaries conductivity on the total conductivity
tional modes are obtained by group theoretical calculations
can be evaluated quantitatively by the blocking factor 𝛼.
developed by Fateley et al. [31]. Factor group analysis of
This parameter characterizes the fraction of the load carriers
Na2 K2 Cu(MoO4 )3 is represented in Table 4. The vibrational
blocked in the case where a direct current flows through the
irreducible representation for the triclinic phase at the center
sample. It can also be calculated using the following equation
of the Brillouin zone (𝑘 = 0) is
[28, 29]:
𝑅gb Γvibr = 57𝐴 𝑔 + 63𝐴 𝑢 , (4)
𝛼= . (3)
𝑅tot
3 acoustic and (3𝑁 − 3) optic modes, where 𝑁 is the number
Figure 5 shows the variation of the blocking factor as a of atoms in the unit cell [32]:
function of the temperature. It is found that the blocking
factor decreases with the temperature. Therefore, the increase Γacoustic = 3𝐴 𝑢
in temperature causes a decrease in the blocking effect by the (5)
limits of the grains. Γoptic = 57𝐴 𝑔 + 60𝐴 𝑢 .
Table 4: Factor group analysis of the triclinic phase Na2 K2 Cu(MoO4 )3 .
Site 𝑛𝑠 𝑡𝛾 𝛾 𝑓𝛾 ∑ Γatom
Atoms 𝜁 𝐶𝜁 𝑎𝜁
symmetry
P-1 𝐴𝑔 1 3
Γtransl Mo1, Mo2, Mo3, Cu1, K2, Na1, Na2, 12 O 𝐶1 2 3 𝐴(𝑇𝑥 , 𝑇𝑦 , 𝑇𝑧 ) 6 19(3𝐴 𝑔 + 3𝐴 𝑢 )
𝑍=2 𝐴𝑢 1 3
𝑍𝐵 = 2 Γtransl K1, K3 𝐶𝑖 1 3 𝐴 𝑢 (𝑇𝑥 , 𝑇𝑦 , 𝑇𝑧 ) 3 𝐴𝑢 1 3 2(3𝐴 𝑢 )
𝑍𝐵 : number of molecules per primitive Bravais cell, 𝑛𝑠 : number of positions, 𝑡𝛾 : number of translations of a site species 𝛾, and 𝑓𝛾 : the degree of vibrational
freedom present in each site species 𝛾.
𝐶𝜁 represents the degeneracy of the species 𝜁 of the factor group, whereas 𝑎𝜁 is the number of lattice vibrations of the equivalent set of atoms in species 𝜁 of the
factor group.
Infrared and Raman active modes are as follows: Point group Td Site group C1 Factor group Ci
Γraman = 57𝐴 𝑔
(6) A 1 ( 1 ) (R) A A g (R) + A u (IR)
Γinfrared = 60𝐴 𝑢 .
E( 2 ) (R) A A g (R) + A u (IR)
In the free state tetrahedral MoO4 ion has 𝑇𝑑 symmetry
and four vibrational modes with the following wavenumbers: A A g (R) + A u (IR)
]1 (𝐴 1 ) nondegenerate symmetric stretching at 936 cm−1 ,
]2 (𝐸) doubly degenerate symmetric bending at 220 cm−1 , F2 ( 3 ) A A g (R) + A u (IR)
]3 (𝐹2 ) triply degenerate asymmetric stretching at 895 cm−1 , (R and IR)
and ]4 (𝐹2 ) triply degenerate asymmetric bending at 365 cm−1 A A g (R) + A u (IR)
[33]. Moreover, all four vibrational modes are active in the
Raman spectra, but only 𝐹2 stretching and bending vibrations A A g (R) + A u (IR)
are active in the IR spectra. However, when this ion is located
in the crystal lattice, its symmetry is lowered due to the F2 ( 4 ) A A g (R) + A u (IR)
constraints imposed by the lattice. So, the local symmetry of (R and IR)
the three MoO4 tetrahedra decreases to 𝐶1 . Because of this A A g (R) + A u (IR)
lowering of symmetry, all modes become active in Raman and
in infrared and degenerate modes raise their degenerations. A A g (R) + A u (IR)
Therefore, ]3 and ]4 are split into three bands 3𝐴 and ]2
into two 2𝐴. The correlation between the point group of 𝑇𝑑 Scheme 1: Correlation scheme for the internal modes of MoO4 in
symmetry of the free anion MoO4 , its site-symmetry 𝐶1 , and Na2 K2 Cu(MoO4 )3 structure.
its factor group 𝐶𝑖 is represented in Scheme 1. According to
Basiev et al. [34], the vibrational modes observed in Raman
spectra of molybdates can be classified into two groups,
internal and external modes. The internal vibrational modes The comparison of the infrared and Raman bands positions
of each type of MoO4 derived from the correlation scheme shows that the majority of these bands do not coincide.
are equal to 𝑍(3𝑛 − 6) = 18, where 𝑛 is the number of atoms Indeed, the observed IR bands appear at wavenumbers
in the molecular MoO4 : different from those in the Raman spectrum (Figure 6).
This is in agreement with the centrosymmetric character
ΓMoO4 = 9𝐴 𝑔 (R) + 9𝐴 𝑢 (IR)
of Na2 K2 Cu(MoO4 )3 structure [36]. The Raman spectrum
can be separated into two parts with a wide empty gap
Γ]1 = 𝐴 𝑔 (R) + 𝐴 𝑢 (IR)
in the range 500–700 cm−1 that is commonly observed in
molybdates containing MoO4 tetrahedra [22, 37–43]. The
Γ]2 = 2𝐴 𝑔 (R) + 2𝐴 𝑢 (IR) (7)
proposed assignment of the vibrational spectra of MoO4 in
Na2 K2 Cu(MoO4 )3 is realised by considering the following
Γ]3 = 3𝐴 𝑔 (R) + 3𝐴 𝑢 (IR)
criteria: ]1 bands are generally very strong in the Raman and
weaker in the infrared spectra, whereas an opposite behavior
Γ]4 = 3𝐴 𝑔 (R) + 3𝐴 𝑢 (IR) .
is usually observed for ]3 bands. ]2 bands are usually stronger
The external vibrational modes of MoO4 are divided into in the Raman spectra than those corresponding to ]4 modes
translational modes which includes acoustic and lattice but in the infrared spectra ]4 band is generally more intense
modes and librational modes [35], presented as follows: [44]. The Mo-O stretching modes are located in the range
720–930 cm−1 whereas the bending modes are situated in the
Γtranslation = Γacoustic + Γlattice = 3𝐴 𝑔 (R) + 3𝐴 𝑢 (IR) range 380–330 cm−1 . Wavenumbers and assignment of the
(8) internal vibrational modes of MoO4 tetrahedron are listed in
Γlibration = 3𝐴 𝑔 (R) + 3𝐴 𝑢 (IR) . Table 5.
100 200 300 400 500 600 700 800 900 1000 1100 boundaries. The blocking effect generated by the limits of
the grains decreases with temperature. The centrosymmetric
space group P-1 of our structure is confirmed by the noncoin-
cidence of majority of Raman and IR bands. Vibrational study
914
indicates the lowering of symmetry of molybdate anion from
𝑇𝑑 to 𝐶1 symmetry.
429 918
Conflicts of Interest
Transmittance (%)
472
Raman intensity
726 789
849 The authors declare that there are no conflicts of interest
regarding the publication of this paper.
891 References
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138 331 344 871
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Original Russian Text © 2018 W. Dridi, M. F. Zid.
CRYSTAL STRUCTURE AND ELECTRICAL

PROPERTIES OF NEW TRIPLE MOLYBDATE
Na0.45K1.55Cu3(MoO4)4
W. Dridi and M. F. Zid
Single crystals of new triple molybdate - sodium potassium copper(II) tetra-[molybdate(VI)]

Na0.45K1.55Cu3(MoO4)4 - are synthesized by a solid-state reaction and its crystal structure is determined. The
compound crystallizes in the monoclinic space group P21/c with a = 5.097(2) Å, b = 14.594(3) Å,
c = 19.905(3) Å, β = 94.00(2)°, V = 1476.9(7) Å3, Z = 4. K2 and Na1 cations are located at the same
general site with occupancies of 0.55 and 0.45 respectively. The structure is formed by infinite Cu3Mo3O23-
type ribbons. These ribbons are connected by a tridentate tetrahedron sharing vertices to build layers
parallel to the (001) plane. All these layers are connected by vertices to form a three-dimensional
framework. The structural model is supported by the bond valence sum. The electrical properties of the title
compound are investigated using complex impedance spectroscopy.
DOI: 10.1134/S0022476618040364
Keywords: solid state, X-ray diffraction, molybdate, electrical properties.
INTRODUCTION
Because of their physicochemical properties, molybdates have received a considerable interest. They have been used
in several application areas: optical technologies [1], piezoelectricity [2], catalysis [3]. Molybdate crystals exhibit
an important structural diversity reported in the literature. They are characterized by mixed frameworks built up from MoO4
and XOn polyhedra (X = transition metal, n = 4-6) with an immense variety of polyhedral connectivity and resulting tunnels
and cavities. Among complex molybdates of interest, there are the alluaudite structure such as Na25Cs8Fe5(MoO4)24 [4], the
glaserite structure such as KAl(MoO4)2 [5], the lyonsite structure such as Li3Al(MoO4)3 [6], the scheelite structure such as
RbSrR(MoO4)3 where R = Nd, Sm, Eu, Gd [7], the NASICON structure such as Na1–xNi1–xSc1+x(MoO4)3, (0 ≤ x ≤ 0.5) [8]. It
is necessary to note that crystals of molybdates with a cationic disorder can have a high ionic conductivity [9]. In this context
we have decided to explore the A–Cu–Mo–O systems (A = monovalent ion). A new phase of the formulation
Na0.45K1.55Cu3(MoO4)4 was obtained by a form melt at 873 K. In this study we report the synthesis, crystal structure, and
electrical properties of Na0.45K1.55Cu3(MoO4)4.
EXPERIMENTAL
Materials and measurements. The X-ray diffraction analysis was performed on an automated four-circle Enraf-
Nonius CAD-4 diffractometer with a graphite-monochromated MoKα radiation source (λ = 0.71073 Å). Electrical
Université de Tunis El Manar, Faculté des Sciences, Laboratoire de Matériaux, Cristallochimie et Thermodyna-
mique Appliquée, Tunis, Tunisie; wassimdridi35@yahoo.fr. The text was submitted by the authors in English. Zhurnal
Strukturnoi Khimii, Vol. 59, No. 4, pp. 1028-1032, May-June, 2018. Original article submitted November 21, 2017.
992 0022-4766/18/5904-0992 © 2018 by Pleiades Publishing, Ltd.
measurements were carried out in air by complex impedance spectroscopy using the Agilent 4294A Precision Impedance
Analyzer in the frequency range 40 Hz–5 MHz and the temperature range 673-833 K. The pellet was prepared by isostatic
pressing at 4 kbar and sintering at 773 K for 12 h in air with 10 K/min heating and cooling rates. The pellet thickness and
surface were about 0.22 cm and 1.25 cm2 respectively with a geometric factor e/s = 0.176 cm–1.
Synthesis of Na0.45K1.55Cu3(MoO4)4 (I). Crystals of I were obtained by a form melt from the following reagents:
Na2CO3, K2CO3, Cu(CO2CH3)⋅H2O, and (NH4)6Mo7O24⋅4H2O with a Na:K:Cu:Mo molar ratio of 0.5:2:3:4. We used a small
amount of a sodium cation to create a random distribution to increase the cation conductivity. The resulting mixture was
milled, and then slowly preheated in air at 623 K for 12 h. Thereafter, it was heated to a temperature close to that of the
fusion at 873 K. It was left at this temperature for two weeks to induce germination and crystals growth.
Single crystal X-ray diffraction. The crystallographic data of I: Na0.45K1.55Mo4Cu3O12, FW = 667.54 g/mol,
T = 293 K, crystal size 0.26×0.22×0.18 mm, triclinic, P21/c, a = 5.097(2) Å, b = 14.594(3) Å, c = 19.905(3) Å, β = 94.00(2),
V = 1476.9(7) Å3, Z = 2, μ(MoKα) = 8.06 mm–1; a total of 3223 reflections (θmin/max = 2.3/27°), 2656 observed reflections
(I ≥ 2σ(I)), 228 parameters, absorption correction (ψ-scan), Tmin/Tmax 0.142/0.235, GOOF = 1.06, Rint = 0.02,
3
R1(I ≥ 2σ(I)) = 0.025, wR2(I ≥ 2σ(I)) = 0.063, max/min diff. peak 0.69/–0.85 e/Å . The structure was solved and refined in
the P21/c space group by direct methods using the SHELXS-97 programs [10] included in the system WinGX publication
[11]. The first refinement cycles permitted us to locate most of atoms. The use of EADP and EXYZ constraints for K2/Na1
located at the same crystallographic site leads to well defined ellipsoids. The maximum and minimum electron densities in
the final Fourier difference map are acceptable and located at 1.41 Å and 0.79 Å, respectively, from the O12 and Na1 atoms.
CIF file containing complete information on the studied structure was deposited with FIZ Karlsruhe, 76344 Eggenstein-
Leopoldshafen, Germany (fax: (+49)7247-808-666; e-mail: crysdata(at)fiz-karlsruhe(dot)de, deposition number CSD-
430925.
RESULTS AND DISCUSSION
Structural study. The structural unit in Na0.45K1.55Cu3(MoO4)4 is formed by three CuO6 octahedra linked by sharing
vertices to four tetrahedra MoO4. The charge compensation is provided by Na+ and K+ cations. The anionic framework is
formed by the succession of two types of endless chains arranged according to the a axis: the first type A consists of an
alternation of Cu1O6 and Cu2O6 octahedra sharing tetrahedra edges. They are linked to Mo4O4 using Mo–Cu–O mixed
bridges. The second infinite chain B is built by the association of Cu3Mo2O12 units. These units were formed by Cu3O6
octahedra and Mo1O4 and Mo2O4 tetrahedra by sharing vertices. The junction between the different polyhedra of the two
chains (A and B) led to infinite ribbons of the Cu3Mo3O22 type. The insertion of Mo3O4 tetrahedra between the ribbons
ensures their junction by sharing vertices. It results in infinite layers orientated parallel to the (001) plane. A disposition in the
opposition phase of these corrugated layers promotes their junction by Mo–Cu–O composite bridges to give a three-
dimensional framework. It presents large elongated cavities where the Na+ and K+ cations reside (Fig. 1). The bond valence
sums calculated [12] from the bond lengths (valence units; Mo1: 5.8924, Mo2: 5.7230, Mo3: layers orientated parallel to the
(001) plane. A disposition in the opposition phase of these corrugated layers promotes their junction by Mo–Cu–O composite
bridges to give a three-dimensional framework. It presents large elongated cavities where the Na+ and K+ cations reside
(Fig. 1). The bond valence sums calculated [12] from the bond lengths (valence units; Mo1: 5.8924, Mo2: 5.7230, Mo3:
5.9474, Mo4: 5.7092, Cu1: 2.0431, Cu2: 2.0598, Cu3: 2.0906, K1: 1.0140, K2/Na1: 1.2376) are close to the expected valence
states of the respective atoms. The studied material is isostructural to AgKCu3(MoO4)4 [13] and K2Cu3(MoO4)4 [14]
compounds. Due to the Jahn-Teller effect [15], the three crystallographically independent copper atoms have a distorted
octahedral coordination (4+2). Indeed, in each octahedron the Cu2+ ion is surrounded by four oxygen atoms at short distances
(1.926 Å to 1.978 Å), which leads to an almost square planar coordination with an average distance of 1.947 Å. These
average distances are similar to those of K4Cu(MoO4)3 compound [16]. The two other Cu–O distances are longer: 2.338 Å to
2.651 Å. The three crystallographically independent molybdenum atoms have a tetrahedral coordination with an average
993
Fig. 1. Projection of the Na0.45K1.55Cu3(MoO4)4 structure
to the a axis.
Mo–O distance of 1.770 Å. This average distance is conform with that of Mo–O in the Na1.51Mg2⋅24(MoO4)3 compound [17].
K2 and Na1 cations are located at the same general site with occupancies of 0.55 and 0.45 respectively. They are surrounded
by seven oxygen atoms with an average K2/Na1–O distance of 2.609 Å. This distance presents a mean between those K–O
distances of the KCoP3O9 compound [18] multiplied by the occupancy rate 0.55 and Na–O distances of NaCo(PO3)3 [19]
multiplied by the occupancy rate 0.45. The K1 cation is surrounded by six oxygen atoms with an average K1–O distance of
2.751 Å.
Electrical properties. The Nyquist plots in the temperature range from 673 K to 733 K shows the presence of two
hardly distinguishable semicircles, which indicates the presence of two relaxation phenomena. The first arc observed towards
higher frequencies corresponds to the movement of ions across the grain (bulk) which represents the intrinsic conduction and
give rise to an intra-granular resistance. The second arc located at a lower frequency corresponds to the ion movement
through the grain boundaries [20]. To explain the electrical behavior of our compound, we use an equivalent electrical circuit
formed by two cells arranged in series, constituted by the parallel combination of the following: R1||C1 and R2||CPE1
corresponding to the contributions of grains and grain boundaries, respectively. R1 and R2 are the resistances of grains and
grain boundaries, respectively. C1 is the pure capacitance of grain and CPE1 is the fractal capacitance constant phase element
according to the grain boundary. To improve the simulation in the temperature domaine ranging from 733 K to 833 K we
have considered the electrode effects. Indeed, the evolution of –Z″ = f(Z′) curves with temperature shows the addition of
a third relaxation low frequency responsible for the polarization of the electrodes. A third cell R3||C2 was therefore added.
Electrical parameters were measured as a function of temperature. The intercepts of the semi-circular arcs with the real axis
give an estimation of the resistance of the studied material. The Zview software [21] was used to fit these curves. The
conformity between the experimental and calculated curves proves the choice of the modeled equivalent circuit (Fig. 2). The
electrical parameters are presented in Table 1.
In order to determine the direct conductivity for the grain interior σg, the grain boundary σgb, and the total
conductivity σtot, we used the equation: σi = e/Ri⋅s (Table 2).
The activation energies were obtained by the linear fitting of the ionic conductivity values at different temperatures
by applying the Arrhenius equation: σ = σ0exp(–EB/KBT), where σ is the temperature-dependent ionic conductivity, σ0 is the
ionic conductivity at absolute zero temperature, Ea is the activation energy of cation migration, KB is the Boltzman constant,
and T is the absolute temperature. The activation energy values in the temperature range from 673 K to 713 K are
994
Fig. 2. Complex impedance spectra of Na0.45K1.55Cu3(MoO4)4 at various temperatures.
TABLE 1. Simulated Data of the Electrical Parameters for the Proposed Equivalent Circuit
T, K Rg, Ω C g, F Rgb, Ω–1 Cgb, F Rel, Ω Cel, F ∑Ri, Ω
673 39724 7.17⋅10–12 949610 6.58⋅10–11 989334

693 38818 6.94⋅10–12 838680 7.40⋅10–11 877498
713 29464 6.64⋅10–12 568690 8.52⋅10–11 598154
733 18725 6.12⋅10–12 202080 7.06⋅10–11 16247 5.72⋅10–9 237052
753 10380 6.50⋅10–12 91255 8.47⋅10–11 9483 4.94⋅10–9 112380
773 6415 5.89⋅10–12 37515 8.29⋅10–11 5313 5.16⋅10–9 50277
793 4115 5.72⋅10–12 18309 9.83⋅10–11 2765 8.34⋅10–9 25189
811 3052 5.66⋅10–12 10299 1.01⋅10–10 1580 1.44⋅10–8 14931
833 2457 5.93⋅10–12 5605 8.62⋅10–11 739.9 1.94⋅10–8 8801.9
TABLE 2. Values of Ionic Conductivities (Ω, cm–1) in the Na0.45K1.55Cu3(MoO4)4 Material
T, K σg σgb σel σtot T, K σg σgb σel σtot
673 4.43⋅10–6 1.85⋅10–7 1.77⋅10–7 773 2.95⋅10–5 4.50⋅10–6 3.33⋅10–5 3.50⋅10–6

693 4.53⋅10–6 2.09⋅10–7 2.00⋅10–7 793 4.27⋅10–5 9.61⋅10–6 6.36⋅10–5 6.98⋅10–6
713 5.97⋅10–6 3.09⋅10–7 2.94⋅10–7 811 5.76⋅10–5 1.70⋅10–5 1.11⋅10–4 1.17⋅10–5
733 9.40⋅10–6 8.70⋅10–7 1.08⋅10–5 7.42⋅10–7 833 7.16⋅10–5 3.14⋅10–5 2.37⋅10–4 1.99⋅10–5
753 1.67⋅10–5 1.91⋅10–6 1.79⋅10–5 1.56⋅10–6
Ea(g) = 0.36 eV, Ea(gb) = 0.58 eV, and Ea(tot) = 0.57 eV. In the temperature range from 713 K to 833 K, they are Ea(g) = 1.17 eV,
Ea(gb) = 2.04 eV, and Ea(tot) = 1.88 eV. From 733 K to 833 K, Ea(el) = 0.71 eV (Fig. 3). We note that the total conductivity of
our compound is less than the bulk conductivity, but higher than the grain boundary one. This reveals the existence of
a partial blockage of charge carriers by the grain boundaries [22]. Accordingly, the conductivity of our compound is limited
by the low conductivity of the grain boundaries.
995
Fig. 3. Arrhenius plot of conductivity of the
Na0.45K1.55Cu3(MoO4)4 sample.
CONCLUSIONS
The Na0.45K1.55Cu3(MoO4)4 compound was characterized by X-ray diffraction and complex impedance spectroscopy.
It crystallized in the P21/c space group. The ionic conductivity of our material is limited by the low conductivity of the grain
boundaries.
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18. Y. Ben Smida, A. Guesmi, S. Georges, and M. F. Zid. J. Solid State Chem., 2014, 221, 278-284.
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Journal of Structural Chemistry. Vol. 59, No. 5, pp. 1128-1132, 2018.
Original Russian Text © 2018 W. Dridi, M. F. Zid.
CRYSTAL STRUCTURE OF NEW ONE-DIMENSIONAL

TRIPLE MOLYBDATE Na2K2Cu(MoO4)3
W. Dridi and M. F. Zid
The title compound (disodium dipotassium copper(II) tris-[molybdate (VI)]) is prepared by form melt and
characterized by single crystal X-ray diffraction and UV-vis spectroscopy. It crystallizes in the triclinic
space group P-1 with a = 7.4946(8) Å, b = 9.3428(9) Å, c = 9.3619(9) Å, α = 92.591(7)°, β = 105.247(9)°,
γ = 105.496(9)°, V = 604.7 Å3, and Z = 2. Its structure is isotypic with that of Na4Mn(MoO4)3. It is formed
by Cu2O10 distorted bi-octahedral dimers linked by two bridging bidentate Mo2O4 tetrahedra and,
additionally, two monodentate Mo1O4 tetrahedra to form Cu2Mo4O20 units. These units are linked by the
insertion of Mo3O4 tetrahedra to build infinite ribbons disposed along the c axis. All of these ribbons form
a one-dimensional framework. Both K1 and K3 cations are located in the inversion center, and all the other
atoms are at general positions. The structure model is supported by the bond valence sum (BVS) and charge
distribution CHARDI methods. The Cu2+ cations adopt the [4+2] CuO6 Jahn-Teller distortion giving rise to
an intense d–d transition in the UV-vis absorption spectra.
DOI: 10.1134/S0022476618050153
Keywords: solid state, X-ray diffraction, bond valence analysis, triple molybdate, charge distribution.
INTRODUCTION
The growing demand for energy in our society represents a challenge for the industrial sector. Moreover, the energy
production and storage is a field that requires the design and development of new effective materials, economic and
ecological and with well-defined structural properties that influence the nature of the ionic conductivity. The chemistry of
oxides has been rapidly developed. This increase can be explained by several agents, essentially, by improving the X-ray
structural diffraction analysis which represents a fundamental tool of the structural resolution. Molybdates with various
combinations of cations have been studied in several experimental works [1]. Many of them are known to be multifunctional
materials with various useful properties for modern applications, such as the ionic conductivity [2], laser [3-5] and
piezoelectric materials [6], photocatalytic and catalytic activities. Indeed, studies concerning the MoO 24 − tetrahedral groups
have shown that they are active for hydrocarbon oxidation [7-9]. According to this approach, we chose to explore A–Cu–Mo–
O systems (A = monovalent ion). We obtained a new formulation structure Na2K2Cu(MoO4)3 by a form melt at 803 K. In this
study we report the crystal structure and UV-vis spectra of new triple molybdate Na2K2Cu(MoO4)3. The structural model is
additionally supported by the bond valence sum (BVS) and charge distribution (CHARDI) methods.
Université de Tunis El Manar, Faculté des Sciences, Laboratoire de Matériaux, Cristallochimie et

Thermodynamique Appliquée, Tunis, Tunisie; wassimdridi35@yahoo.fr. The text was submitted by the authors in English.
Zhurnal Strukturnoi Khimii, Vol. 59, No. 5, pp. 1168-1172, June-July, 2018. Original article submitted October 19, 2017.
1128 0022-4766/18/5905-1128 © 2018 by Pleiades Publishing, Ltd.

EXPERIMENTAL
Materials and measurements. The X-ray diffraction analysis was performed on an automated four-circle Enraf-
Nonius CAD-4 diffractometer with a graphite-monochromated MoKα radiation source (λ = 0.71073 Å). An optical absorption
spectrum of the title compound was acquired from a Shimadzu 3100S UV-vis-NIR spectrometer. The UV-vis diffuse
reflectance spectrum of I was taken in the range from 300 nm (4.13 eV) to 1800 nm (0.68 eV). Data were collected in the
reflectance (% R) mode and manually converted to arbitrary absorption units (u.a) by the relationship A = –log(R) [10].
Synthesis of Na2K2Cu(MoO4)3 (I). Crystals of I were obtained by a form melt at 803 K from the following
reagents: Na2CO3, K2CO3, Cu(CO2CH3)⋅H2O, and (NH4)6Mo7O24⋅4H2O with a Na:K:Cu:Mo molar ratio of 2:2:1:3. The
resulting mixture was milled in an agate mortar, placed in a porcelain crucible, and then slowly preheated in air at 350 °C for
24 h. Thereafter, the mixture was heated to a temperature close to that of the fusion at 530 °C. It is left at this temperature for
one week to induce germination and crystals growth. Green crystals of suitable size were chosen under polarizing microscope
for the structure determination and refinement.
Single crystal X-ray diffraction. The crystallographic data on I: Na2K2Mo4O12, FW = 667.54 g/mol–1, T = 298 K,
crystal size 0.24×0.18×0.12 mm, triclinic, P–1, a = 7.4946(8), b = 9.3428(9), c = 9.3619(9) Å, α = 92.591(7), β = 105.247(9),
γ = 105.496(9)°, V = 604.7 Å3, Z = 2, μ(MoKα) = 3.666 mm–1, a total of 2629 reflections (θmin / θmax = 2.3 / 27°), 2342
observed reflections (I ≥ 2σ(I)), 185 parameters, absorption correction (ψ-scan), Tmin / Tmax 0.311 / 0.511, GOOF = 1.08,
Rint = 0.014, R1(I ≥ 2σ(I)) = 0.022, wR2(I ≥ 2σ(I)) = 0.056, max / min diff. peak 0.66 / –0.97 e/Å3. The structure was solved
and refined unambiguously in the P-1 space group by direct methods using the SHELXS-97 programs [11] included in the
system WinGX publication [12]. The first refinement cycles permitted us to locate most of atoms. The refinement of all
variable parameters leads to well defined ellipsoids. The maximum and minimum electron densities in the final Fourier
difference map are acceptable and located at 0.73 Å and 0.94 Å, respectively, from the O4 and Mo2 atoms. CIF file
containing complete information on the studied structure was deposited with FIZ Karlsruhe, 76344 Eggenstein-
Leopoldshafen, Germany (fax: (+49)7247-808-666; e-mail: crysdata(at)fiz-karlsruhe(dot)de, deposition number CSD-
430379.
RESULTS AND DISCUSSION
Structural study. The structural unit in Na2K2Cu(MoO4)3 is built from a CuO6 octahedron connected by pooling
three of its vertices to three MoO4 tetrahedra. The charge compensation is provided by Na+ and K+ cations (Fig. 1). Every two
juxtaposed octahedra in the anionic framework are bound by sharing an edge to form dimer type Cu2O10. The latter connects
with two bidentate Mo2O4 tetrahedra by Mo–O–Cu double composite bridges and with monodentate Mo1O4 tetrahedra by
Mo–O–Cu simple ones to form Cu2Mo4O20 units (Fig. 2a). Cu2Mo4O20 units are connected by inserting Mo3O4 tetrahedra
and pooling vertices to form ribbons arranged according to the [100] direction (Fig. 2b). All these ribbons form a one-
dimensional framework with inter-ribbons spaces containing monovalent Na+ and K+ cations directed to the free vertices of
the MoO4 tetrahedra (Fig. 3). The studied material is isostructural to the K4Mn(MoO4)3 compound [13]. The three
crystallographically independent molybdenum atoms have tetrahedral coordination with average Mo–O distances of
1.758(3) Å, 1.768(3) Å, and 1.764(3) Å for Mo(1), Mo(2), and Mo(3) respectively. These values are similar to those found in
the literature [14]. The copper atom has a distorted octahedral (4+2) environment due to the Jahn-Teller effect [15, 16].
Indeed, four oxygen atoms are located at short distances from the copper atom (1.93 Å to 2.01 Å), which leads to an almost
square planar coordination with an average distance of 1.976 Å; this average distance is consistent with Cu–OIV in the
Cu9Na6(PO4)8 compound [17]. The two other Cu–O distances are longer: 2.296 Å and 2.438 Å. The average Cu–OVI distance
is 2.07(3) Å. These bond lengths are similar to those found in the literature [18, 19]. The K+ cations occupy three
crystallographically independent sites (K1, K2, and K3) with different O-atom environments. Indeed, K1 and K3 cations are
1129
Fig. 1. Coordination polyhedra in the structural unit in
Na2K2Cu(MoO4)3. All atoms are represented as
displacement ellipsoids at the 50% probability level.
[Symmetry codes: i –x, –y+1, –z+1; ii –x+1, –y+1, –z+1].
Fig. 2. Representation of the Cu2Mo4O20 unit (a); Fig. 3. Projection of the Na2K2Cu(MoO4)3 structure to
projection of a ribbon along the b axis (b). the a axis.
surrounded by ten oxygen atoms, but K2 is coordinated by nine oxygen atoms. The Na+ cations occupy two
crystallographically independent sites (Na1 and Na2) with the octahedral environment. The proposed structural model is
confirmed by two validation models: BVS [20] and the charge distribution (CD)) method [21, 22]. The CD method is the
most recent development of Pauling’s concept of the bond strength [23]. Instead of empirical parameters used in the BVS
1130
approach, it exploits the experimental bond lengths deduced from the structural study to compute a non-integer coordination
number, ECoN (effective coordination number), around a PC atom (atom placed at the center of a polyhedron, q > 0), which
is coordinated by V atoms (atoms located at the vertices, q < 0); q is the formal oxidation number. ECoN takes into account
not only the number of V atoms around a given PC atom, but also their weight in terms of relative distances. Calculated
charges Q(i) and valences V(i) are in good agreement with the formal oxidation number (q) multiplied by occupancy rates.
The dispersion factor MAPD is 1.5% for the calculated cationic charges. The results of the two validation models are
summarized in Table 1.
UV-Vis diffuse reflectance. The spectrum of Na2K2Cu(MoO4)3 contains a broad and intense low-energy absorption
band centred at an energy of 1.30 eV. It is attributed to the Laporte-forbidden d–d transitions 2Eg → 2T2g of a distorted
octahedral (4+2) coordination of copper [24]. The second absorption band at high energy from 2.15 to 4.13 eV corresponds to
the O(p)–Cu(d) ligand-to-metal charge transfer (LMCT) [25]. The energy gap determined from the intersection of the tangent
to the absorbance curve and the horizontal axis of energies is 2.19 eV (Fig. 4). Therefore, our material has a semiconductor
behaviour.
TABLE 1. CHARDI and BVS Analysis of Cation Polyhedra in Na2K2Cu(MoO4)3
Cation q(i), sof(i) Q(i) V(i) CN(i) ECoN(i) dar dmed
Mo1 6.000 5.95 6.095 4 3.98 1.758 1.758

Mo2 6.000 5.93 5.731 4 3.96 1.769 1.769
Mo3 6.000 6.13 5.802 4 3.97 1.765 1.764
Cu1 2.000 2.04 1.980 6 4.68 2.106 2.106
K1 1.000 0.96 1.038 8 6.84 2.870 2.870
K2 1.000 0.99 0.932 9 7.96 2.962 2.961
K3 1.000 0.96 1.140 8 6.54 2.845 2.845
Na1 1.000 1.00 0.997 6 5.85 2.430 2.430
Na2 1.000 1.00 1.003 6 5.76 2.430 2.430
q(i) = formal oxidation number, sof(i) = site occupation factor, Q(i) = calculated charges, CN = coordination
number, ECoN = number of effective coordination, dar = arithmetic average distance, dmed = weighted average distance,
100 qi − Qi
MAPD = ∑ iN .
N qi
Fig. 4. UV-Vis spectrum of Na2K2Cu(MoO4)3.
1131
CONCLUSIONS
In this work we have synthesized a novel molybdate compound of the composition Na2K2Cu(MoO4)3 by a solid state
reaction. This material was characterized by single crystal X-ray diffraction and UV-vis spectroscopy. It crystallized in the
triclinic symmetry with the P-1 space group. The structure of Na2K2Cu(MoO4)3 is formed by Cu2Mo4O20 units linked by the
insertion of MoO4 tetrahedra to build infinite ribbons along the c axis. The structural model is assessed by BVS and CD
methods.
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1132
Solid State Sciences 136 (2023) 107106
Contents lists available at ScienceDirect
Solid State Sciences

journal homepage: www.elsevier.com/locate/ssscie
Ac conductivity and modulus behavior of

K0.12Na0.54Ag0.34Nb4AsO13 compound
Saïda Fatma Chérif a, b, *, Wassim Dridi a, Amira Chérif c, Samia Nasr d, e, Mounir Ferhi f,
Mohamed Faouzi Zid a
a
Chemistry Department, Faculty of Sciences of Tunis, Laboratory of Materials, Crystal Chemistry and Applied Thermodynamics, Tunis El Manar University, El Manar II,
2092, Tunisia
b
University of Tunis El Manar, Preparatory Institute for Engineering Studies, BP 244 El Manar II, 2092, El Manar, Tunis, Tunisia
c
Laboratoire Matériaux, Organisation et Propriétés, Faculté des Sciences de Tunis, Université de Tunis El Manar, 2092, El Manar II, Tunis, Tunisia
d
Department of Chemistry, Faculty of Sciences and Arts Touhama, King Khaled University,Muhayil, Asir, 63311, Saudi Arabia
e
Electrochemistry, Materials and Environment, Preparatory Institute for Engineering Studies, Kairouan, 3100, Tunisia
f
Physico-Chemistry Laboratory for Mineral Materials and Their Applications, National Center for Research in Materials Sciences (CNRSM), Borj Cedria Technopole,
8027, Soliman, Tunisia
A R T I C L E I N F O A B S T R A C T
Keywords: Some physical properties of K0.12Na0.54Ag0.34Nb4AsO13 powder, synthesized visa a solid-state reaction at 800 ◦ C,
Impedance spectroscopy are discussed in this study. The vibrational analysis verifies the existence of the AsO3− 7−
4 and NbO6 functional
Ionic conductivity groups. The X-ray powder diffraction pattern and Rietveld refinement confirm the formation of a pure phase that
Dielectric properties
crystallizes in an orthorhombic system with a Cmcm space group. The structure and chemical composition of the
Modulus analysis
Ac conductivity
compound are studied using the Scanning Electron Microscopy and the Energy Dispersive Spectroscopy. Complex
impedance spectroscopy is used to examine the electrical conductivity, dielectric properties and relaxation
behavior of the aforementioned compound at different temperatures and across the 0.01 kHz–13 MHz frequency
range. The correlation between K0.12Na0.54Ag0.34Nb4AsO13’s crystalline structure and its ionic conductivity is
also studied.
1. Introduction a three-dimensional framework with tunnels where the mobile cations

are stored [11,14,15,20]. Additionally, we find compounds with
The arsenates and phosphates materials containing a monovalent two-dimensional framework that contains interlayer spaces containing
cation have attracted researchers because of their ionic conduction and monovalent cations [12,13].
magnetic behavior, two properties that point to their potential useful Our previous work detailed the synthesis and crystal structure of the
ness in a variety of fields [1–5]. In recent years, sodium-ion batteries are compound under discussion [20], which can be visualised as infinite
considered as the most attractive alternative to lithium-ion batteries chains of (Nb(1)O6–Nb(1)O6–As (1)O4) arranged along [100] (Fig. 1(a)).
owing to the chemical similarities between Li and Na ions, the wide The connection between these strings is secured by sharing octahedra
spread abundance of sodium as well as its low cost compared to the edge Nb(2)O6 (Fig. 1(b)). The resulting three-dimensional framework
lithium element [6–10]. For this reason, we have looked into the A – defines large cavities, with hexagonal section, containing cations of
Nb–As – O systems (A is an alkali and/or pseudo-alkali metal), which sodium, silver and potassium (Fig. 1(c)).
contain a vast number of materials with a wide range of structure types, Powdered K0.12Na0.54Ag0.34Nb4AsO13 was prepared and a Rietveld
such as Na3Nb4As3O19 [11], Na2AsNbO6 [12], Na3As2NbO9 [13], refinement was carried out using the single crystal structure data [20] in
NaAsNb2O8 [14], NaAsNb4O13 [15], K8Nb7As7O39 [16], K0.8Ag0.2N the 2θ range 5–70◦ . Both the electrical and dielectric properties at
b4O9AsO4 [17], Ag0.62K0.38Nb4AsO13 [18], Ag3Nb(NbO)2O4(AsO4)2 temperatures between 240 and 500 ◦ C and in the frequency range of
[19] and K0.12Na0.54Ag0.34Nb4AsO13 [20]. Some of these arsenates have 0.01 kHz–13 MHz were investigated.
* Corresponding author. Chemistry Department, Faculty of Sciences of Tunis, Laboratory of Materials, Crystal Chemistry and Applied Thermodynamics, Tunis El
Manar University, El Manar II, 2092, Tunisia.
E-mail address: c.fatouma@yahoo.fr (S.F. Chérif).
https://doi.org/10.1016/j.solidstatesciences.2022.107106
Received 12 November 2022; Received in revised form 17 December 2022; Accepted 27 December 2022
Available online 29 December 2022
1293-2558/© 2022 Elsevier Masson SAS. All rights reserved.
S.F. Chérif et al. Solid State Sciences 136 (2023) 107106
Fig. 1. (a) Representation of strings, (b) junction between channels and (c) projection of the structure along c axis showing tunnels where Na+, Ag+ and K+ cations
are located.
Fig. 2. EDS spectrum and SEM micrograph of K0.12Na0.54Ag0.34Nb4AsO13.
2
2.1. Characterization techniques of K0.12Na0.54Ag0.34Nb4AsO13
The chemical composition and the crystal morphology were

confirmed by means of the Energy Dispersive Spectroscopy (EDS) and
the Scanning Electron Microscopy (SEM) using a FEI Quanta 200 FEG
scanning electron microscope. Fig. 2 illustrates the data that were
collected; the EDS spectrum shows the expected elements to be present
including Ag, Na, K, Nb, As and O.
The coordination environment of the title compound was studied by
means of infrared spectroscopy in the range 300–1200 cm− 1 at room
temperature using a PerkinElmer FTIR Paragon 1000 PC spectrometer.
KBr was added to the sample and shaped as cylindrical pellet. A PAN-
analytical X’Pert PRO X-ray diffractometer with a copper anticathode
(λKα = 1.5406 Å) was used to conduct a room-temperature X-ray powder
diffraction analysis on the obtained powder. Electrical measurements
were taken in the frequency range of 0.01 kHz–13 MHz and tempera
tures of (240–500) ◦ C in the open atmosphere using a Hewlett-Packard
4192-A automatic bridge and an HP microcomputer. To improve grain
Fig. 3. FTIR spectrum of K0.12Na0.54Ag0.34Nb4AsO13.
continuity, the powder was pressed at 12 tonnes to create a pellet
(diameter = 13 mm, thickness = 1.99 mm), which was then heated to
500 ◦ C for 12 h. After the pellet was prepared, silver electrodes were
Table 1
painted onto both sides to ensure good electrical contact. To testify the
Proposed assignment of the IR modes of
K0.12Na0.54Ag0.34Nb4AsO13. existence of phase transition, the differential Scanning Calorimetry
(DSC) analysis was carried out over the temperature range 25–620 ◦ C
Wavenumber (cm− 1) Assignment
(step: 10 ◦ C/min).
422 ν4(AsO4)
482 ν4(NbO6)
3. Results and discussion
655 ν3(NbO6)
730
842 ν1(AsO4) 3.1. Vibrational properties
921 ν3(AsO4)
966 Fig. 3 depicts the infrared spectrum of K0.12Na0.54Ag0.34Nb4AsO13
1095
compound, which was recorded in the domain containing the expected
principal vibrations. Based on previous studies [16,18,21–27], Table 1
2. Experimental details compiles the assignments of observed vibrational bands of the NbO6 and
AsO4 groups.
2.1. Chemical preparation of K0.12Na0.54Ag0.34Nb4AsO13
All chemicals, commercially available, were used without any 3.2. Structural characterization
further purification.
Conventional solid-state reaction technique was applied to synthe The Rietveld refinement method was applied to the X-ray powder
size the K0.12Na0.54Ag0.34Nb4AsO13 compound as monocrystalline diffraction data of K0.12Na0.54Ag0.34Nb4AsO13 sample using the avail
powder from a stoichiometric mixture of K2CO3 (Fluka, 99%), AgNO3 able single crystal structure data [20] and PullProf software. Fig. 4
(Prolabo, 99.8%), Na2CO3 (Sigma-aldrich, ≥99.5%), As2O5 (Merck, displays the final Rietveld plot. The obtained reliability factors show
99%) and Nb2O5 (Fluka, ≥99.9%). Starting materials were mixed and that the observed and calculated profiles agree well, which points to the
ground together in an agate mortar and heated progressively to 800 ◦ C formation of a pure single-phase powder.
in porcelain crucible with intermittent cooling and re-grindings.
Fig. 4. The Rietveld refinement result of K0.12Na0.54Ag0.34Nb4AsO13 sample.
3
Fig. 5. Nyquist plots (- Z′′ vs. Z′) of K0.12Na0.54Ag0.34Nb4AsO13 over temperature range 240 and 500 ◦ C.
3.3. Electrical properties

Table 2
Simulated electrical parameters for the proposed equivalent circuit.
Complex impedance spectroscopy (CIS), the dominant technique for
T (◦ C) T (K) Rg (Ω) Cg (F) Rgb (Ω) Cgb (F) Rtotal (Ω) characterizing such materials, was used to study the compound’s elec
240 513 330,430 5.450.10− 9 444,060 1.637.10− 8 774,490 trical properties.
260 533 249,180 1.841.10− 9 340,850 8.83.10− 9 590,030 In the Nyquist plots (Fig. 5), the line observed at low frequency is
280 553 229,290 1.709.10− 9 293,740 7.679.10− 9 523,030
attributed to the phenomenon of polarization at the electrodes which
300 573 181,100 1.787.10− 9 289,820 1.342.10− 8 470,920
320 593 139,260 1.827.10− 9 212,350 1.219.10− 8 351,610
confirms the existence of an ionic conduction. We observe, at high fre
340 613 99,505 1.874.10− 9 168,610 2.094.10− 8 268,115 quency, two hardly distinguishable semicircles corresponding to the two
360 633 85,751 1.953.10− 9 162,830 2.596.10− 8 248,581 relaxation processes generated from the diffusion of the ions through the
380 653 67,782 1.99.10− 9 134,470 3.546.10− 8 202,252 grains (g) and the grain boundaries (gb) [28,29].
400 673 54,663 2.192.10− 9 122,420 5.208.10− 8 177,083
The resistances characteristic of these contributions can be refined
420 693 42,110 2.072.10− 9 58,163 7.958.10− 7 100,273
440 713 24,285 2.194.10− 9 28,939 1.124.10− 7 53,224 separately thanks to the equivalent electric model consisting of three
460 733 17,054 2.393.10− 9 20,018 2.164.10− 7 37,072 cells. These latter are arranged in series and formed by the parallel
480 753 12,151 2.358.10− 9 13,843 3.375.10− 7 25,994 combination of the following: Rg || Cg, Rgb || Cgb and CPE1 corre
500 773 8243 1.947.10− 9 11,348 2.929.10− 7 19,591
sponding to the contributions of grains, grains boundaries and polari
zation at the electrodes, respectively. Rg and Rgb are the resistances of
Fig. 6. Complex impedance diagram in the Nyquist plane for K0.12Na0.54Ag0.34Nb4AsO13 recorded at (a): 320 ◦ C and (b) 500 ◦ C. The inset presents the equivalent
electrical circuit used for experimental data fitting.
4
Table 3
Ionic conductivities (σg, σbg and σtot) of K0.12Na0.54Ag0.34Nb4AsO13 phase.
σi = t / Ri .s (1)
T (◦ C) T (K) Conductivity (Ω− 1.cm− 1) The effect of the temperature on the ionic conductivity of the grains
σg σbg σtotal
according to the equation log (σT) = f (1000/T) shows that it follows an
7
Arrhenius type law expressed by equation (2) where A is the pre-
240 513 4.50928.10− 3.3554.10− 7 2.27246.10− 7
7 exponential factor, Ea is the activation energy and kB is the Boltzmann
260 533 5.97961.10− 4.37142.10− 7 2.98290.10− 7
280 553 6.49832.10− 7

5.07251.10− 7 3.36501.10− 7 constant.
7
300 573 8.22750.10− 5.14112.10− 7 3.73737.10− 7 ( )
6 Ea
320 593 1.06994.10− 7.01672.10− 7 5.00555.10− 7
σ.T = A.exp − (2)
6
340 613 1.49741.10− 8.83696.10− 7 6.56435.10− 7 kB .T
6
360 633 1.73759.10− 9.15065.10− 7 7.08019.10− 7
380 653 2.19822.10− 6

1.10805.10− 6 8.70202.10− 7 The variation of (Ln (σT)) versus 103/T is represented in Fig. 7. Two
400 673 2.72579.10− 6
1.21712.10− 6 9.93884.10− 7 linear regions, presenting different slopes, were noticed. The values of
420 693 3.53835.10− 6
2.56177.10− 6 1.75521.10− 6
the activation energy, calculated though the slope of each temperature
6
440 713 6.13547.10− 5.14876.10− 6 3.30678.10− 6
region, are collected in Table 4.
6
460 733 8.73695.10− 7.44330.10− 6 4.01920.10− 6
5 The total conductivity was found lower than both the grain and grain
480 753 1.22623.10− 1.07635.10− 5 5.73209.10− 6
500 773 1.80759.10− 5

1.31300.10− 5 7.60553.10− 6 boundaries conductivity. However, the total activation energy was
found lower than the bulk one and higher than the grain boundary value
at low temperature range (513–673) K. This result was also observed by
Ben Said et al. [32] that confirm the presence of a partial blockage of the
charge carriers by the grain boundaries. For high temperature range, the
total activation energy was found higher than the bulk one and lower
than the grain boundaries value.
Fig. 8 shows the variation of real part of the impedance (Z′ ) with
frequency at different temperatures. A rise of both frequency and tem
perature induces a decrease of Z′ values, thus, an increase of the ac
conductivity [33]. Besides, Z′ values merge at higher frequency (HF) to
become independent of frequency and that for all investigated temper
atures. This behavior can be attributed to the reduction in barrier
properties that leads to the release of space charge when T increases
[34–36]. Then, at low frequency (LF), a semiconductor like behavior
was observed (a decrease of Z′ when T increases) [37].
Fig. 9 illustrates the variation of (- Z′′ ), the imaginary part of the
impedance, in terms of frequency for temperatures ranging from 240 to
500 ◦ C (step 20 ◦ C). For each temperature, a one broad asymmetric peak
was observed. It is clear that Z′′ values increased with the frequency until
it reached a maximum (- Z′′ max) then decreased with the temperature.
Add to this, Z′′ values shifted to higher frequency when the temperature
rises which indicates a temperature dependency of the relaxation time in
Fig. 7. Arrhenius plots of conductivity of
K0.12Na0.54Ag0.34Nb4AsO13 as observed for polycrystalline samples: Ni
K0.12Na0.54Ag0.34Nb4AsO13 sample.
(1–3%) – ZnO [38], Sb2O4 [39], Ni0.6+xZn0.2Cu0.2VxFe2− 2xO4 (0.0 ≤ x ≤
0.25) [40] and 0.95(K0.5Na0.5)NbO3–0.05BaTiO3 ceramic [41].
Table 4
Activation energies in K0.12Na0.54Ag0.34Nb4AsO13 material.
3.4. Modulus analysis
Contribution Temperature range (K) Ea (eV)
Grains 513–673 0.388 On the basis of the electric modulus’s physical properties, we dis
673–773 0.929
cussed a possible relationship between the conductivity and the ionic
Grains boundaries 513–673 0.290
673–773 1.132 relaxation in the title compound [42,43]. This latter can be expressed as
Total 513–673 0.325 [44,45]: M* = M’ + j M′′ where M’ = – ωC0Z′′ and M’’ = ωC0Z’ are the
673–773 1.055 real and the imaginary parts of the electrical modulus respectively (ω =
2πf is the angular frequency, Z′ is the real part of the impedance, Z′′ is the
imaginary part of the impedance and C0 = ε0.S/e).
grains and grains boundaries, respectively. Cg, Cgb and CPE1 are the
The frequency dependence of M′ at different temperatures is given in
capacitance of grain, grains boundaries and the fractal capacitance
Fig. 10. As can be seen, at LF, M′ tends to zero for all investigated
constant phase element respectively [30]. The total resistance Rtotal =
temperatures indicating that the electrode polarization makes a negli
Rg + Rgb as well as electrical parameters are gathered in Table 2.
gible contribution [46]. However, M′ reached its maximum value in the
The equivalent circuit choice was validated by the close agreement
HF region. The conductivity relaxation process might be responsible for
between the experimental and the calculated curves throughout the
the dispersion between these frequencies [47,48]. Charge carriers’
studied temperature range (Fig. 6). For each diagram, the values of re
limited range of motion could be responsible for the continuous spread
sistances and CPE used are refined using the ZView software [31]. Thus,
seen at HF [49].
making it possible to determine the values of the corresponding ionic
M′′ vs. f curves for the different temperatures are shown in Fig. 11.
conductivities. The direct conductivity for the grain σg, grain boundary
Relaxation peaks that shift toward to H-frequencies as the temperature
σgb as well as the total conductivity σtotal, were calculated using equation
rises were highlighted. The non-Debye type of relaxation can be inferred
(1) where t is the thickness of the patch (cm) and s is its surface (cm2).
from the asymmetry in peak broadening, which reveals the distribution
The obtained values are gathered in Table 3.
of relaxation times with different time constants [50]. This latter is also
supported by the representation of M′′ vs. M′ plots in the temperature
5
Fig. 8. Frequency dependence of real part of the impedance at different temperatures.
6
Fig. 9. Variation of the imaginary part of the impedance in terms of frequency for temperature range of (240–500) ◦ C.
7
Fig. 10. Frequency dependence of real part of electric modulus.
8
Fig. 11. Frequency dependence of the imaginary part of electric modulus.
is the imaginary part of relative permittivity, f is the frequency of the

applied field and ω = 2πf is the angular frequency.
σac = ωε0 ε′′ = 2πf ε0 ε′′ (3)

Fig. 13 depicts the frequency dependence of the Ac conductivity at
different temperatures. Ionic materials typically exhibit a dc plateau in
the LF region and an increase in conductivity with an increase in fre
quency. In the LF range, it is found that the conductivity does not depend
on the frequency. Jonscher’s universal power law [51] (4), where A is
the pre-exponential factor, σdc is the dc conductivity (frequency inde
pendent plateau in the LF region) and the exponent n can take values
between 0 and 1, is commonly used to analyze the phenomenon of the
conductivity dispersion.
σ(w) = σdc + Awn (4)
Using the conductivity value at 1000 Hz, as presented in Fig. 14, it
was found that the conductivity exhibits a thermally activated behavior
[52,53] in accordance with the Arrhenius relation [54–60] (5) where
σ0 is a pre-exponential factor, Ea is the activation energy related with
Fig. 12. Complex modulus plots at the temperature range [440− 500] ◦ C. this conduction process, kB is the Boltzmann constant and T is the
temperature.
range of [440− 500] ◦ C which reveals that the semicircles are depressed σ = σ0 exp( − Ea / kB .T) (5)
(Fig. 12).
The obtained values of activation energies are: Ea = 1.002 eV and Ea
3.5. Electrical conductivity analysis = 0.251 eV at high and low temperatures respectively.
The plot of conductivity variation as a function of the inverse of
Ac conductivity, which was calculated using the following relation temperature for the title compound (Fig. 14) shows a kink at T = 400 ◦ C.
(3), was used to investigate the ionic transport properties of This behavior is generally related to a phase transition, an appearance of
K0.12Na0.54Ag0.34Nb4AsO13, where ε0 is the permittivity of free space, ε’’ second mechanism of ionic conductivity or a change of the conduction
9
Fig. 13. Frequency dependence of the ac conductivity at various temperatures.
occurring at different frequencies exhibit a single conduction mecha

nism and the conductivity relaxation process is temperature indepen
dent [61,62]. The close activation energies values determined from
Arrhenius plots (Fig. 14) and the variation of Ln (σdc) (Fig. 7) in each
temperature range indicate that ionic conduction was due to transport
through ion hopping mechanism in the investigated materials [62,63].
Therefore, the kink at 400 ◦ C and the slope change observed in the
Arrhenius plots can be explained as follows.
- Appearance of second pathway coupled to the chain structure of the

title compound formed by three –dimensional framework. So, the
high temperature induces the chain structure vibration and great
dynamic disorder which leads to more than one pathway for ion
hopping [63].
- Hopping of Na + at low temperature followed by hopping of K+ at
high temperature, which are located alternately in the wide tunnels
of the studied material.
3.6. Correlation between electrical and structural properties

Fig. 14. The variation of Ln (σdc) versus 103/T.
The ionic conductivity of K0.12Na0.54Ag0.34Nb4AsO13 compound was
pathways. To testify the first hypothesis, the Differential Scanning investigated using ion-mobility promoting conditions. Structure-based
Calorimetry (DSC) analysis was carried out over the temperature range explanations for these phenomena include.
25–620 ◦ C. The obtained results as well as a zoom in the range
330–460 ◦ C are reported in Fig. 15. At 400 ◦ C, DSC thermogram do not • The 3D framework of the structure.
presents any phase transition or other thermal phenomenon which ex • The presence of tunnels with hexagonal section where potassium,
cludes the existence of phase transition. sodium and silver cations are located.
Frequency dependence of the imaginary part of electric modulus • The cations occupy partially their sites.
(Fig. 11) shows a near overlapping of curves on a single ‘master curve’
for all the temperatures. This indicates that the dynamic processes There are tunnels in the structure where housed the potassium,
10
Fig. 15. DSC analysis curve of K0.12Na0.54Ag0.34Nb4AsO13 over the temperature range 25–620 ◦ C. The inset represents a zoom from 330 to 460 ◦ C.
K0.12Na0.54Ag0.34Nb4AsO13 compound synthesized via a solid state re

action at 800 ◦ C. Dielectric relaxation, modulus behavior and conduc
tion mechanism were discussed in terms of both temperature and
frequency. Similar activation energy, deduced from impedance spectra
and σdc conductivity, were found revealing that the relaxation process
may be attributed to the same type of charge carriers and the same
conduction mechanism based on ion hopping process. The thermal
variation of ac and dc conductivity of the material follows Arrhenius
type of electrical conductivity.
Author statement
Saïda Fatma Chérif: sample synthesis, conceptualization, writing-

original draft. Wassim Dridi and Amira Chérif: conductivity study.
Samia Nasr: Writing review. Mounir Ferhi: DRX measurements, discus
sion. Mohamed Faouzi Zid: supervision, discussion.
Declaration of competing interest
Fig. 16. Dimensions of the hexagonal tunnel in The authors declare that they have no known competing financial
K0.12Na0.54Ag0.34Nb4AsO13 structure. interests or personal relationships that could have appeared to influence
the work reported in this paper.
Table 5 Data availability

Positions and occupancies of Ag+, Na+ and K+ cations in
K0.12Na0.54Ag0.34Nb4AsO13. The data that has been used is confidential.
Atoms x y z Occupancies
Ag1 0 − 0.0486 (8) 0.2165 (6) 0.173 (4)

Acknowledgements
K1 0 − 0.057 (3) 0.067 (9) 0.059 (13)
Na1 0 − 0.0472 (18) 0.160 (32) 0.268 (13) This work is supported by the Ministry of Higher Education and
Scientific Research of Tunisia.
sodium and silver cations; their dimensions are 5.316 Å and 6.057 Å as
References
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12
Arabian Journal of Chemistry (2020) 13, 5627–5638
King Saud University
Arabian Journal of Chemistry

www.ksu.edu.sa
www.sciencedirect.com
ORIGINAL ARTICLE
Ac conductivity, electric modulus analysis,

dielectric behavior and Bond Valence Sum analysis
of Na3Nb4As3O19 compound
Saı̈da Fatma Chérif a,b,*, Amira Chérif c, Wassim Dridi a, Mohamed Faouzi Zid a
a
Laboratoire de Mate´riaux, Cristallochimie et Thermodynamique Appliqueé, Faculte´ des Sciences de Tunis, Universite´ de Tunis
El Manar, 2092 El Manar II, Tunis, Tunisia
b
Institut Pre´paratoire aux Etudes d’Ingeńieurs – El Manar, Universite´ de Tunis El Manar, 2092 El Manar II, Tunis, Tunisia
c
Laboratoire Mate´riaux, Organisation et Proprie´te´s, Faculte´ des Sciences de Tunis, Universite´ de Tunis El Manar, 2092 El Manar
II, Tunis, Tunisia
Received 31 December 2019; accepted 2 April 2020

Available online 10 April 2020
KEYWORDS Abstract The Na3Nb4As3O19 compound is synthesized by solid state reaction method and charac-
Dielectric properties; terized by X-ray diffraction. The structure is described as a three-dimensional anionic framework
Modulus analysis; having two kinds of tunnels where sodium cations are located. The framework of the title com-
Ac conductivity; pound is thus of open character and the motion of sodium cations through the tunnels seems to
BVS analysis be feasible. This factor led us to study the ionic conduction. In this work, we present the dielectric
and electrical properties of Na3Nb4As3O19 compound by using the complex impedance spec-
troscopy technique, in the frequency range 0.01 – 13000 kHz. The conductivity measurements of
the obtained ceramic are studied over a temperature range from 300 to 620 °C. The real and imag-
inary parts of the dielectric constant were found to decrease with frequency and to increase with
temperature. The values of the frequency of the maximum of the imaginary part of the modulus
and of the impedance are different indicating a non-Debye type of relaxation process. The values
of the activation energy (Ea) calculated by different methods are in conformity. The Bond Valence
Sum (BVS) model is used to identify the conduction pathways for the monovalent cations, allowing
a better correlation between the electrical and the structural data. It suggests that the most probable
sodium conduction pathway is along c-direction.
Ó 2020 Published by Elsevier B.V. on behalf of King Saud University. This is an open access article under
the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
* Corresponding author at: Laboratoire de Matériaux, Cristallochimie et Thermodynamique Appliquée, Faculté des Sciences de Tunis,
Université de Tunis El Manar, 2092 El Manar II, Tunis, Tunisia.
E-mail address: c.fatouma@yahoo.fr (S.F. Chérif).
Peer review under responsibility of King Saud University.
Production and hosting by Elsevier
https://doi.org/10.1016/j.arabjc.2020.04.003
1878-5352 Ó 2020 Published by Elsevier B.V. on behalf of King Saud University.
This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
5628 S.F. Chérif et al.
1. Introduction and their potential applications in several domains. They can

exhibit ionic conduction properties, magnetic performances
The arsenates compounds containing a monovalent cation . . . (Ben Amor et al., 2008; Ben Smida et al., 2015; Chérif
have attracted researchers due to their physical properties et al., 2011, 2012; Falah et al., 2015; Marzouki et al., 2014;
Ouerfelli et al., 2007, 2015). Add to this, materials with open
framework built up from polyanion groups like AsO4 are con-
Table 1 Characteristics of the used chemicals. sidered as cationic conductor compounds in positive electrode
in lithium batteries. In particular, LiCoAsO4 arsenate with oli-
The used chemicals Purity (%) Manufacturers vine structure (Arroyo-de Dompablo et al., 2006) shows inter-
Na2CO3 99,5 Sigma-aldrich esting electrochemical properties. Where, Li-ions was
As2O5 99 Merck reversibly deinserted / inserted from/into material at average
Nb2O5 99,9 Fluka voltages of 4.8 and 4.6 V respectively. In addition, the delithi-
ated material maintaining the olivine structural framework.
Fig. 1 Calculated and experimental powder X-ray diffraction patterns of Na3Nb4As3O19.
Fig. 2 Frequency dependence of real part of the impedance at different temperatures.

Ac conductivity, electric modulus analysis, dielectric behavior and Bond Valence Sum 5629
Fig. 3 Variation of the imaginary part of the impedance as a function of frequency at several temperatures.
Fig. 4 Normalized imaginary part of impedance Z00 / Z00 max for Na3Nb4As3O19 compound as a function of frequency at the temperature
range 300 – 620 °C.
For this reason, we have investigated the Na – Nb – As – O crystal form via a solid state reaction at 800 °C (Chérif
systems in which, at the best of our knowledge, only five et al., 2012). The structural study showed that the arsenate pre-
materials were synthesized: Na2AsNbO6 (Hizaoui et al., sents two types of tunnels where Na+ cations are located. The
1999), Na3As2NbO9 (Hizaoui et al., 1999), NaAsNb2O8 concept of bond valence can be successfully used to simulate
(Harrison et al., 1994), NaAsNb4O13 (Bestaoui et al., 1998) cations migration in the crystal bulk. In this case, the BVS
and Na3Nb4As3O19 (Chérif et al., 2012). Four of these com- model offers a useful tool to relate the novel crystal structure
pounds exhibit a three dimensional framework characterized to its ionic conductivity properties.
by the presence of tunnels in which sodium cations are located. The present work is devoted in the first part to study the
Only the first one have a layer structure where Na+ cations are electrical and dielectric properties of Na3Nb4As3O19 at the
located between the covalent [NbAsO6]2 layers in hexagonal temperature range 300 – 620 °C and in the frequency domain
channels. For the last one, it was synthesized in a single- of 0.01 – 13000 kHz and in the second part to simulate the
transport pathway of sodium ions by using the Bond Valence
Sum model (BVS).
2. Experimental details
All chemicals were commercially available and were used with-

out any further purification. The characteristics of the used
chemicals for the preparation of the studied compound in
forms of monocrystals or polycrystalline powders are collected
in Table 1.
Single crystals and the polycrystalline powder of the title
compound were obtained by a solid state reaction as men-
tioned in previous works (Chérif et al., 2012, 2019).
The Na3Nb4As3O19 compound was characterized by single
crystal X-ray diffraction. It crystallizes in the orthorhombic
system, space group C2221 with a = 13.014(2) Å,
Fig. 5 Arrhenius plot of Ln (s) versus 104 / T. b = 24.170(3) Å, c = 5.0880(9) Å and Z = 4. Add to this,
Fig. 6 Frequency dependence plot of real part of dielectric constant.

it was characterized by X-ray powder diffraction technique 8c, 8c, 8c and 8c respectively) as determined by X-ray diffrac-
using a PAN-analytical X’Pert PRO X-ray diffractometer tion. Analysis occurred along initial migration directions such
equipped with copper anticathode (kKa = 1.5406 Å). Fig. 1 as [1 0 0], [0 1 0] and [0 0 1] towards crystallographic sites, fol-
shows the X-ray diffraction patterns of the calcined powder lowing the lowest bond valence sum Vi(x, y, z). Points in this
recorded at room temperature and the calculated one. All valence map with the lowest Vi(x, y, z) values correspond to
the reflection peaks of the XRD pattern were indexed and lat- stable positions; the highest values are associated with
tice parameters refined using Celref 3.0 program (Altermatt bottlenecks.
and Brown, 1987). The best agreement was found in an
orthorhombic system (C2221 space group) and the refined least
squares lattice parameters are: a = 13.015(2) Å, b = 24.175(4) 3. Results and discussion
Å and c = 5.0857(1) Å which are in good agreement with the
literature (Chérif et al., 2012). 3.1. Impedance spectroscopy analysis
The electrical measurements were carried with a
Hewlett-Packard 4192-A automatic bridge monitored by a The electrical properties of Na3Nb4As3O19 compound have
HP microcomputer in the frequency range 0.01–13000 kHz at been investigated using complex impedance spectroscopy.
(300 – 620 °C) temperature range. More details concerning the Fig. 2 shows the variation of real part of the impedance (Z0 )
preparation of the samples are given in previous work (Chérif with frequency at different temperatures. We note that the
et al., 2019). In order to study the electric properties of this com- value of Z0 decreases with rise of both frequency and temper-
pound, we have modeled the complex impedance spectra using ature which suggests an increase in the ac conductivity (Saif
Zview software (ZView Version 3.1c, 1990 - 1997) and the best and Poopalan, 2011).
fit is obtained when employing an equivalent electrical circuits At low frequency, the values of Z0 decrease with rise in tem-
formed by a parallel combination of bulk resistance and CPE; perature showing behavior similar to that of semiconductors
which is the non-ideal capacitor usually known as constant (Suman et al., 2006). However, for all temperatures and at high
phase element (Anantha and Hariharan, 2005). frequency, the Z0 values merge and then become independent
Bond Valence Sum Vi(x, y, z) is calculated for a grid of of frequency, this is may be due to the release of space charge
points (x, y, z) starting from Na1, Na2, Na3, Na4, Na5, resulting from the reduction in barrier properties of the mate-
Na6, Na7 and Na8 crystallographic positions (4a, 4a, 4a, 4a, rial (Postnikov et al., 1970).
Fig. 7 Frequency dependence plot of imaginary part of dielectric constant.

The variation of the imaginary part of the impedance (- Z00 ) equal to those inferred from conductivity analysis (Chérif
as a function of frequency at different temperatures is shown in et al., 2019).
Fig. 3. We observe the presence of one broad asymmetric peak
at each temperature, the Z00 values increased with the fre- 3.2. Dielectric study
quency, reached a maximum (- Z00 max) and then decreased.
Add to this, - Z00 max values shifted to higher frequency when The dielectric response in a solid material can be described by
the temperature rises. This is an indication of the temperature expressing the relative dielectric constant as a complex
dependency of the relaxation time in such polycrystalline sam- quantity made up of a real and an imaginary components:
ple (Mhamdi et al., 2014). e* = e0 – j e00 , where e0 and e00 are respectively the real and
The normalized spectra of the imaginary part of impe- imaginary part of the dielectric constant, representing the
dance (Z00 / Z00 max) as a function of frequency are repre- amount of energy stored in a dielectric material as polarization
sented in Fig. 4. The presence of a single relaxation peak and the energy loss, while applying an electric field (Hassan
indicates a thermally activated process that passes though et al., 2012; Xie et al., 2019, 2020; Shi et al., 2019).
a maximum at s which is the relaxation time (Liu et al., The real part of the dielectric constant (e0 ) can be calculated
2008, 2009; Dang et al., 2016, 2017). s is calculated using from complex impedance data by using the relation (3):
the formula (1): 00
Z
s ¼ 1=2pfmax ð1Þ e0 ¼ 0 ð3Þ
x:C0 ðZ}2 þ Z 2 Þ
00 00
where fmax is the peak frequency of Z / Z max. This relaxation
time plotted as a function of the reciprocal temperature is The imaginary part of the dielectric constant (e00 ) can be
shown in Fig. 5. It can be seen that the relaxation time s obeys obtained by the Eq. (4):
0
to the Arrhenius law (2): Z
e00 ¼ 02
ð4Þ
s ¼ s0 expðEa =kB :TÞ ð2Þ x:C0 ðZ}2 þ Z Þ
where s0, kB, T and Ea are respectively the pre-exponential fac- where Z0 , Z00 , x and C0 are respectively the real part of the
tor, the Boltzmann constant, the absolute temperature and the impedance, the imaginary part of the impedance, the angular
activation energy. frequency and the geometrical capacitance.
The activation energies were calculated from the slope and Fig. 6 shows the frequency dependence of e0 at different
were found to be: Ea(1) = 0.96 eV and Ea(2) = 0.37 eV at high temperatures from 300 to 620 °C.
and low temperatures respectively. It is noteworthy that the First, at constant temperature, the dielectric constant
activation energy values deduced from relaxation time are decreases with the increase of frequency. This behavior can
Fig. 8 Frequency dependence of real part of electric modulus.

be assigned to the fact that, at low frequencies, all types of e00 ¼ rac =e0 :x ð5Þ
polarizations contribute to the dielectric constant value, as in the frequency range studied since the ac conductivity can be
deformational polarization (electronic, ionic) and relaxation
confused with the dc conductivity in low frequency.
(orientation and interfacial). We note that, at low frequencies,
the orientation and interfacial polarizations are very impor-
3.3. Electrical modulus analysis
tant. Add to this, for all temperatures, the e0 values merge at
higher frequency, this is may be due to electronic and ionic
polarizations which are temperature independent. At high fre- The electrical modulus formalism is used to study the electrical
quency, e0 reached a constant value due to interfacial relaxation mechanism in ion conducting materials (Mtioui
polarization. et al., 2015). The advantage of this formalism is that the elec-
Second, at constant frequency, the dielectric constant trode polarization effects are suppressed.
increases with the increase of temperature. This behavior can The electrical modulus can be expressed using the relation
be explained by the fact that the dipoles cannot orient them- (Soares et al., 2006) (6):
selves at low temperatures. When the temperature increased, M ¼ M0 þ jM00 : ð6Þ
the orientation of dipoles is facilitated, which tends to an
increase in dielectric constant value. The real and the imaginary parts of the complex electrical
Fig. 7 shows the frequency dependence of e00 at different modulus were calculated using the following expressions:
temperatures from 300 to 620 °C. e00 decreases by increasing M0 = – xC0Z00 and M00 = xC0Z0 .
frequency, at constant temperature and increases by increasing Fig. 8 shows the frequency dependence of the real part of
temperature at constant frequency. The imaginary part of electric modulus (M0 ) at different temperatures. It was
dielectric constant consists of the contribution for the dc con- observed that, at low frequencies, M0 approaches to zero at
duction at low and moderate frequencies. When the tempera- all temperatures which indicates that electrode polarization
ture increases the conductivity increases which leads to the makes a negligible contribution (Chatterjee and Gupta,
high value of the dielectric constant, e00 . This is in agreement 2012). However, at higher frequencies, M0 displays a maximum
with the relation (5): value. The dispersion in between these frequencies may be due
to the conductivity relaxation process (Dutta et al., 2008). A
continuous dispersion on increasing frequency may be due to
Fig. 10 The variation of Ln(fmax) versus 104 / T.
Fig. 9 Frequency dependence of the imaginary part of electric

modulus. Fig. 11 Frequency response of M00 and – Z00 at 300 °C.
the short range mobility of charge carriers (Behera et al., a non-Debye relaxation is confirmed with short-range move-
2007). ment of charge carriers (Cao and Gerhardt, 1990).
The variation of the imaginary part of electric modulus
(M00 ) as a function of frequency at several temperatures is 3.4. Electrical conductivity analysis
shown in Fig. 9. The plots of this figure are characterized by
the presence of relaxation peak. The peak shifts toward to
Ac conductivity measurement is an important tool for study-
higher frequency as the temperature is raised. The observed
ing the ionic transport properties of materials. It’s calculated
asymmetry in peak broadening indicates the spread of relax-
using the following relation (8):
ation time with different time constant which supports the
non-Debye type of relaxation in the material (Kaur et al., rac ¼ xe0 e00 ¼ 2pfe0 e00 ð8Þ
2016).
The value of the peak frequency fmax has been determined where f is the frequency of the applied field, e00 is the imaginary
for each temperature, the variation of Ln(fmax) as a function part of the dielectric constant, x = 2pf is the angular fre-
of temperature is shown in Fig. 10. It appears to satisfy the quency and e0 is the permittivity of free space.
Arrhenius law governed by the relation (7):
fmax ¼ f0 expðEa = kB :TÞ ð7Þ
where f0 is the pre-exponential factor and Ea is the activation
energy for the relaxation process. The Arrhenius plot
shows two slopes, the value of activation energies are:
Ea(1) = 0.97 eV in the temperature region 440 – 480 °C and
Ea(2) = 0.37 eV in the temperature range 300 – 440 °C.
Values of Ea calculated from conductivity and from the
modulus spectra are close, suggesting that the mobility of the
charge carrier is probably due to a hopping mechanism
(Sahoo et al., 2013; Ren et al., 2019).
Fig. 11 shows the frequency response of – Z00 and M00 at
T = 300 °C. For an ideal Debye type relaxation with long-
range movement of charge carriers, the fmax values of both
impedance and modulus plots at any temperature should coin-
cide. From these plots, this is not the case for our sample, thus Fig. 13 The variation of Ln(rdc) versus 104 / T.
Fig. 12 Frequency dependence of the ac conductivity at various temperatures in a log-log scale.

Fig. 14 Bond valence sum for sodium ions: (a) Na1, (b) Na2, (c) Na3, (d) Na4, (e) Na5, (f) Na6, (g) Na7 and (h) Na8 versus the covered
distance.
Fig. 12 shows the frequency dependence of the ac conduc- rðxÞ ¼ rdc þ Axn ð9Þ
tivity for Na3Nb4As3O19 at different temperatures. It exhibits where rdc is the dc conductivity (frequency independent pla-
the typical behavior of ionic materials: the conductivity is teau in the low frequency region), A is the temperature depen-
found to be frequency independent in the low frequency (dc dent factor and n is the frequency exponent of the mobile ions.
plateau) which increases with the increase of the frequency. Using the value of the conductivity at 100 Hz, as presented
The phenomenon of the conductivity dispersion is generally in Fig. 13, it was found that the conductivity exhibits a ther-
analyzed using the Jonscher’s universal power law (Jonscher, mally activated behavior (Khan and Hogarth, 1991) in accor-
1991) (9): dance with the Arrhenius relation (Hummel, 1998) (10):
r ¼ r0 exp ð Ea = kB :TÞ ð10Þ low compared to the other cations. Furthermore, the mobility
where r0 is a pre-exponential factor, Ea is the activation energy of all cations is easy along the [0 0 1] direction, the direction of
related with this conduction process, kB is the Boltzmann con- the tunnels. Indeed, the maximum valence reached according
stant and T is the temperature. to this direction for Na1, Na2, Na3, Na4 and Na5 cations is
There are two linear regions with two different slopes. The respectively 1.18, 1.34, 1.17, 1.34 and 0.78 v.u for migration
values of Ea have been determined from the slope of two distance in the order of 10 Å. For Na6, Na7 and Na8, the max-
straight lines of two different temperature regions. The imum valence is 0.8 v.u for migration distance in the order of
obtained values are: Ea(1) = 0.93 eV and Ea(2) = 0.38 eV at 8, 8.8 and 9.5 Å respectively.
high and low temperatures respectively. Along [1 0 0] and [0 1 0] directions, the Na2, Na3 and Na4
ions motion seems difficult and the cations reach quickly bot-
tlenecks: Vumax attains a value more than 2 v.u for short dis-
3.5. Conduction pathway proposed from Bond valence Sum
tances which does not exceed 2 Å. The same finding was
observed for Na1 cation along a cell direction.
The BVS (Brown, 1987) model finds one of its applications in For Na5, Na6, Na7 and Na8 cations, their mobility is not
the correlation between crystal structure and its ionic conduc- easy along [1 0 0] and [0 1 0] directions: these cations reach
tivity properties. It allows to identify the mobile species and to quickly bottlenecks: Vumax attains a value more than 1.8 v.u
propose conduction mechanisms. This model was used with for migration distance in the order of 11 Å. The same finding
success to determine the migration pathways of different spe- of Vumax was observed for Na1 cation along b cell direction,
cies such as lithium ion in Li2/3-xLa3xTiO3 (Mazza et al., but for migration distance in the order of 3 Å.
2002), LiLa(PO3)4 (Ferhi et al., 2012), sodium ion in NaCo2- BVS analysis was in agreement with the suggestions derived
As3O10 (Ben Smida et al., 2015), Na4Co5.63Al0.91(AsO4)6 from the data of structural study. In fact, the most probable
(Marzouki et al., 2013), Na3.5Cr1.83(AsO4)3 (Fakhar conduction pathway is hence along [0 0 1] direction: direction
Bourguiba et al., 2014), NaLuP2O7 (Béjaoui et al., 2014), of the two kinds of tunnels where Na+ cations are located. The
Ag1.6Na1.4Al2(AsO4)3 (Fakhar Bourguiba et al., 2012), BVS modeling results can materialize the migration paths in
NaHoP2O7 (Béjaoui et al., 2013), silver ion in Ag3Nb(NbO)2- the probable directions. These pathways are shown in Fig. 15.
O4(AsO4)2 (Ben Amor et al., 2008), Ag1.6Na1.4Al2(AsO4)3
(Fakhar Bourguiba et al., 2012) and potassium ion in
4. Conclusion
KFeAs2O7 (Ouerfelli et al., 2007).
The variation of the valence as a function of the distance
traveled by Na+ cations in our compound Na3Nb4As3O19 is This work covers some physical properties of Na3Nb4As3O19
reported in Fig. 14. The BVS analysis shows that the initial compound obtained via a solid state reaction at 800 °C. Dielec-
valence of Na1, Na2, Na3, Na4, Na5, Na6, Na7 and Na8 tric relaxation, modulus behavior and conduction mechanism
cations is respectively 0.96, 1.03, 1.06, 1.11, 0.78, 0.78, 0.76 have been investigated in terms of both temperature and fre-
and 0.75 v.u (valence unit). This value is relatively high for quency. The non-coincidence of peaks corresponding to mod-
Na4 which shows that the mobility of this cation should be ulus and impedance indicates deviation from Debye-type
Fig. 15 Schematic representation of the sodium conduction pathways along the [0 0 1] direction.
relaxation. The values of the activation energy of the com- Dang, J., Liu, L., Sun, X., Liu, S., Yan, T., Fang, L., Elouadi, B.,
pound (calculated from both impedance and modulus spectra) 2017. Dielectric relaxation behavior and mechanism of Y2/3Cu3-
are very similar, suggesting that the relaxation process may be Ti4O12 ceramic. J. Adv. Dielectr. 88, 320–329.
attributed to the same type of charge carriers. On the basis of Dang, J., Sun, X., Liu, S., Liu, L., Yan, T., Fang, L., Elouadi, B.,
2016. Influence of interface point defect on the dielectric properties
BVS analysis, we can conclude that the transport properties in
of Y doped CaCu3Ti4O12 ceramics. J. Adv. Dielect. 6 (1), 1650009.
this material appear to be due to Na+ ions movement along c Dutta, A., Sinha, T.P., Jena, P., Adak, S., 2008. Ac conductivity and
direction. The movement along [1 0 0] and [0 1 0] directions dielectric relaxation in ionically conducting soda-ime-silicate
seems to be difficult. glasses. J. Non-Cryst. Solids. 354, 3952–3957.
Fakhar Bourguiba, N., Gusemi, A., Ouerfelli, N., Mazza, D., Zid, M.
Acknowledgements F., Driss, A., 2012. Le nouvel arséniate Ag1. 6Na1.4Al2(AsO4)3:
synthèse, études structurale et électrique, simulation des chemins de
This work is supported by the Ministry of Higher Education conduction ionique. J. de la Société Chimique de Tunisie. 14, 201–
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and Scientific Research of Tunisia.
Fakhar Bourguiba, N., Ouerfelli, N., Zid, M.F., 2014. Crystal
Structure, Charge-Distribution and Bond-Valence-Sum Investiga-
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research communications
Synthesis, crystal structure and charge-distribution

validation of b-Na4Cu(MoO4)3 adopting the
ISSN 2056-9890
alluadite structure-type
Wassim Dridi and Mohamed Faouzi Zid*
Laboratoire de Matériaux et Cristallochimie, Faculté des Sciences de Tunis, Université de Tunis El Manar, 2092 El Manar
Received 9 June 2016 Tunis, Tunisia. *Correspondence e-mail: faouzi.zid@fst.rnu.tn
Accepted 27 June 2016
Single crystals of a new variety of tetrasodium copper(II) tris[molybdate(VI)],

Edited by T. J. Prior, University of Hull, England Na4Cu(MoO4)3, have been synthesized by solid-state reactions and character-
ized by single-crystal X-ray diffraction. This alluaudite structure-type is
Keywords: crystal structure; BVS; CHARDI; characterized by the presence of infinite layers of composition (Cu/Na)2Mo3O14
alluaudite-type; sodium; copper(II); molybda- parallel to the (100) plane, which are linked by MoO4 tetrahedra, forming a
te(VI). three-dimensional framework containing two types of hexagonal channels in
which Na+ cations reside. The Cu2+ and Na2+ cations are located at the same
CCDC reference: 1487800
general site with occupancies of 0.5. All atoms are on general positions except
for one Mo, two Na (site symmetry 2) and another Na (site symmetry 1) atom.
Supporting information: this article has
supporting information at journals.iucr.org/e One O atom is split into two separate positions with occupancies of 0.5. The title
compound is isotypic with Na5Sc(MoO4)4 and Na3In2As3O12. The structure
model is supported by bond-valence-sum (BVS) and charge-distribution
CHARDI methods. -Na4Cu(MoO4)3 is compared and discussed with the
K4Cu(MoO4)3 and -Na4Cu(MoO4)3 structures.
1. Chemical context
In recent years, a number of molybdates have received
considerable attention due to their amazing properties and
high application potential in various fields, such as photo-
luminescence (Shi et al., 2014) and Li-ion batteries (Reddy et
al., 2013). For example, the copper molybdate Cu3Mo2O9
doped with lithium displays high Coulombic efficiency in
lithium-ion batteries and excellent charge-discharge stability
(Xia et al., 2015). Many new molybdate phases have been
synthesized and structurally characterized by X-ray diffrac-
tion, among which a large number belong to the alluaudite
type, such as Na25Cs8Fe5(MoO4)24, which presents a high
electrical conductivity (Savina et al., 2014). The alluaudite-
type structure was first determined on natural minerals by
Fisher, who showed that alluaudite compounds crystallize in
the monoclinic C2/c space group (Fisher, 1955). Moore
proposed the general formula X(2)X(1)M(1)M(2)2(PO4)3, in
which the X and M mono-, bi- or trivalent cations are written
according to their size (X are large cations and M are distorted
octahedrally coordinated atoms). It represents the parental
structure-type of the group referred to as alluaudite-type
(Moore, 1971). The size of the channel and the stability of the
alluaudite network led to many phases belonging to this
structural type. We can totally or partially replace not only the
monovalent cations, but also the central atoms of the MO6
octahedra and TO4 tetrahedra. It is also possible to make
substitutions with cations in different oxidation states
adopting the same type of coordination number (Mo6+, V5+,
Acta Cryst. (2016). E72, 1103–1107 http://dx.doi.org/10.1107/S2056989016010367 1103

Table 1
Selected bond lengths (Å).
Mo1—O1 1.746 (3) Na2—O5iv 2.462 (3)
Mo1—O5 1.762 (3) Na2—O5 2.549 (3)
Mo1—O2i 1.764 (3) Na2—O5ii 2.549 (3)
Mo1—O6 1.774 (3) Na3—O41vii 2.443 (7)
Mo2—Mo2ii 0.447 (2) Na3—O41viii 2.443 (7)
Mo2—O41 1.456 (7) Na3—O1ix 2.493 (3)
Mo2—O3ii 1.738 (3) Na3—O1ii 2.493 (3)
Mo2—O41ii 1.740 (7) Na3—O1vi 2.675 (3)
Mo2—O4 1.787 (7) Na3—O1x 2.675 (3)
Mo2—O3 1.822 (3) Na3—O4vii 2.749 (7)
Mo2—O4ii 2.150 (6) Na3—O4viii 2.749 (7)
Cu1—O4iii 1.884 (6) Na3—O41xi 3.008 (7)
Cu1—O3 2.098 (3) Na3—O41xii 3.008 (7)
Cu1—O2 2.116 (3) Na4—O3 2.337 (2)
Cu1—O6 2.152 (3) Na4—O3xiii 2.337 (2)
Cu1—O5iv 2.317 (3) Na4—O2 2.424 (3)
Figure 1 Cu1—O6v 2.464 (4) Na4—O2xiii 2.424 (3)
Representation of the coordination polyhedra in the structural unit of - Cu1—O41iii 2.467 (4) Na4—O1v 2.490 (4)
Na4Cu(MoO4)3, showing (a) full atomic, (b) polyhedral. All atoms are Na2—O5vi 2.462 (3) Na4—O1xiv 2.490 (4)
represented as displacement ellipsoids at the 50% probability level.
[Symmetry codes: (i) x, y, z 1; (ii) x + 1, y, z + 12; (iii) x + 12, y + 12, Symmetry codes: (i) x; y; z 1; (ii) x þ 1; y; z þ 12; (iii) x þ 12; y þ 12; z þ 12; (iv)
x; y; z þ 12; (v) x þ 32; y þ 12; z þ 1; (vi) x þ 1; y; z; (vii) x 12; y þ 12; z 12;
z + 12; (iv) x, y, z + 12; (v) x + 32, y + 12, z + 1.] (viii) x þ 12; y 12; z þ 12; (ix) x 1; y; z 12; (x) x 1; y; z; (xi) x þ 12; y þ 12; z;
(xii) x 12; y 12; z; (xiii) x þ 1; y; z þ 32; (xiv) x 12; y þ 12; z þ 12.
P5+ and As5+). Alluaudite molybdates usually have the general
formula of X(2)X(1)M(1)M(2)2(MoO4)3 and adopt the C2/c Na5Sc(MoO4)4, Na2Ni(MoO4)2 (Klevtsova et al., 1991) and
space group, with a ’ 12, b ’ 13 and c ’ 7 Å, examples being Na2.2Zn0.9(MoO4)2 (Efremov et al., 1975), which crystallize in
the K0.13Na3.87MgMo3O12 (Ennajeh et al., 2015), the space group C2/c with cell parameters of about a ’ 12, b ’
Na3Fe2(MoO4)3 (Muessig et al., 2003) and Na4Co(MoO4)3 13 and c ’ 7 Å. All alluaudite-type compounds can be
(Nasri et al., 2014) compounds. A review of the literature also described by the general formula given by Moore (1971), but
reveals the presence of other formulae, such as their structures can differ by the number of formula units per
unit cell. They are characterized by a three-dimensional
heteropolyhedral framework formed by TO4 tetrahedra and
MO6 octahedra, delimiting two types of channels running
along the c axis. A new variety of -Na4Cu(MoO4)3 formu-
lation was obtained by a reaction in the solid state at 873 K.
2. Structural commentary
The structural unit in -Na4Cu(MoO4)3 is formed by MO6
(M = Cu1/Na1) octahedra linked by sharing vertices with
Mo1O4 tetrahedra and two slightly different Mo2O4 tetra-
hedra, with a partially occupied (0.5 occupancy) Mo2 site.
Atom O4 is split into two separate positions, with occupancies
of 0.5 for the O4 and O41 atoms. The charge compensation is
provided by Na+ cations (Fig. 1). The essential building units
of the structure are M2O10 units obtained from two edge-
sharing MO6 octahedra. These units are connected by Mo1O4
tetrahedra through vertex-sharing via Mo—O—M mixed
bridges. This results in M2Mo2O16 units. Each unit is connected
to six other identical units by the sharing of vertices, leading to
an infinite layer of the M2Mo3O14 type parallel to the (100)
plane (Fig. 2). The linkage of these layers is ensured by the two
slightly different Mo2O4 tetrahedra, linking via corners. This
results in a three-dimensional framework delimited by two
kinds of channels running along the c axis at (12, 0, z) and (0, 0,
z). These channels are occupied by Na+ cations (Fig. 3). In the
anionic framework, each Mo2O4 tetrahedron shares its O
Figure 2 atoms with four different M2O10 dimers belonging to two
A projection of the polyhedral layers in the bc plane. adjacent layers. The Mo1O4 tetrahedron shares only three O
1104 Dridi and Zid Na4Cu(MoO4)3 Acta Cryst. (2016). E72, 1103–1107
Table 2
CHARDI and BVS analysis of cation polyhedra in -Na4Cu(MoO4)3.
Cation q(i)sof(i) Q(i) V(i).sof(i) CN(i) ECoN(i) dar dmed
Mo1 6.00 6.24 5.93 4 4.00 1.761 1.761

Mo2 3.00 2.48 3.06 4 3.52 1.777 1.776
M 1.50 1.75 1.64 6 4.97 2.214 2.214
Na2 1.00 0.98 0.79 4 4.49 2.505 2.703
Na3 1.00 0.83 0.85 8 8.19 2.587 2.670
Na4 1.00 1.24 1.11 6 5.86 2.417 2.417
Notes: M = Cu1/Na1, q(i) = formal oxidation number, sof(i) = site-occupation factor,

Q(i) = calculated charges, CN = coordination number, ECoN = number of effective
coordination, MAPD = 100/NiN.|qi - Qi/qi|, dar = arithmetic average distance and dmed =
weighted average distance.
(Solodovnikov & Solodovnikova, 1997). The Na+ cations

occupy three crystallographically independent sites with
different O-atom environments. The Na2, Na3 and Na4 atoms
are surrounded by four, eight and six O atoms, respectively
(Table 1). The Cu1 and Na1 cations are located at the same
general site, with occupancies of 0.5, and have an octahedral
environment with an average distance of 2.214 Å. This
distance presents a mean between the Na—O distances of
Na2Cu(PO3)4 (Laügt et al., 1972) and the Cu—O distances
encountered in Ag2Cu2(MoO4)3 (Tsyrenova et al., 2009). The
proposed structural model is confirmed by two validation
models: (i) the bond-valence approach using the empirical
Figure 3
A projection of the -Na4Cu(MoO4)3 structure, viewed normal to (001),
showing the channels where monovalent cations are located.
atoms with three M2O10 units belonging to the same layer, the
other O atom being free and pointing towards the channels
where the Na3 cations are located (Fig. 4). There is some
compositional flexibility in the alluaudite structure and the
studied material is isostructural with Na5Sc(MoO4)4 (Klevt-
sova et al., 1975) and Na3In2As3O12 (Khorari et al., 1997). The
two crystallographically independent Mo atoms have tetra-
hedral coordination, with an average Mo—O distance of
1.761 Å for Mo1 and 1.777 Å for Mo2, which is in a good
agreement with those typically observed in Rb2Cu2(MoO4)3
Figure 4
The association modes of M2O10-based units by the (a) Mo(1)O4 and (b) Figure 5
Mo(2)O4 tetrahedra. For clarity, we present only one atom of A projection of the K4Cu(MoO4)3 structure, viewed along the [001]
molybdenum, Mo2. direction.
Acta Cryst. (2016). E72, 1103–1107 Dridi and Zid Na4Cu(MoO4)3 1105
crystallizes in the Pnma space group. Its structure can be
described as being composed of a distorted square-planar
CuO4 polyhedron bound by shared vertices to two Mo1O4
tetrahedra to form CuMo2O10-type units. These units are
interconnected, on the one hand, by insertion of two Mo2O4
tetrahedra which share a face with a partial occupation (0.5
occupancy) of Mo2 atoms, and secondly by forming a mixed
bridge of the Mo—O—Cu type. This forms ribbons arranged
parallel to the [100] direction. This results in a one-dimen-
sional structure in which K+ atoms reside in the inter-ribbon
spaces (Fig. 5). The structure of our new variety -
Na4Cu(MoO4)3 is compared with the variety. Indeed, -
Na4Cu(MoO4)3 (Klevtsova et al., 1991) crystallizes in the
triclinic system, space group P1, and its structure is formed by
the same Cu2O10 dimers present in our structure (here present
as mixed-occupied M2O10 units). The latter connects via Mo—
O—Cu double composite bridges with two bidentate tetra-
hedra MoO4 and by Mo—O—Cu simple bridges with mono-
dentate MoO4 tetrahedra to form Cu2Mo4O20 units. The
Cu2Mo4O20 units are connected by MoO4 tetrahedra and the
pooling of vertices to form ribbons arranged in the [010]
direction. All the ribbons form a one-dimensional framework
with inter-ribbon spaces containing monovalent Na+ cations
(Fig. 6). This structure has the same arrangement of structural
units found in the one-dimensional structure of K3Mn(MoO4)3
(Solodovnikov et al., 1998) (Fig. 7).
3. Synthesis and crystallization

-Na4Cu(MoO4)3 crystals were obtained by a solid-state
Figure 6 reaction from the following reagents: Na2CO3 (Prolabo,
A projection of the -Na4Cu(MoO4)3 structure, viewed in the (010) plane. 70128), Cu(CO2CH3)H2O (Sigma–Aldrich, C5893) and
(NH4)6Mo7O244H2O (Sigma–Aldrich, 13301) with an
formula of Brown (Brown & Altermatt, 1985) and (ii) the Na:Cu:Mo molar ratio of 4:1:3. The resulting mixture was
charge-distribution method Chardi (Nespolo, 2015, 2016). The
charge distribution method is the most recent development of
Pauling’s concept of bond strength (Pauling, 1929). Instead of
empirical parameters used in the bond-valence approach, it
exploits the experimental bond lengths deduced from the
structural study to compute a non-integer coordination
number, ECoN (effective coordination number), around a PC-
atom (atom placed at the center of a polyhedron, q > 0), which
is coordinated by V atoms (atoms located at the vertices, q <
0); q is the formal oxidation number. ECoN takes into account
not only the number of V atoms around a given PC atom, but
also their weight in terms of relative distances. Calculated
charges Q(i) and valences V(i) are in good agreement with the
formal oxidation number (q) multiplied by occupancy rates.
The dispersion factor MAPD, which measures the mean
absolute percentage deviation, is 2.2% for the calculated
cationic charges. The variation of the ECoN value to the
traditional coordination indicates the degree of distortion. The
two validation models results are summarized in Table 2.
Comparing our structure with that of a similar formulation, i.e.
K4Cu(MoO4)3 (Menard et al., 2011), we found a clear differ-
ence, on the one hand, in the crystal symmetry and, on the Figure 7
other hand, in the arrangement of polyhedra. K4Cu(MoO4)3 A projection of the K4Mn(MoO4)3 structure, viewed normal to (010).
1106 Dridi and Zid Na4Cu(MoO4)3 Acta Cryst. (2016). E72, 1103–1107
Table 3 leads to well-defined ellipsoids. The maximum and minimum
Experimental details. electron densities in the final Fourier difference map are
Crystal data acceptable and located at 0.77 and 0.82 Å, respectively, from
Chemical formula Na4Cu(MoO4)3 the Na2 and Mo1 atoms.
Mr 635.32
Crystal system, space group Monoclinic, C2/c
Temperature (K) 298
a, b, c (Å) 12.5318 (9), 13.8181 (9), 7.1159 (7)
( ) 111.95 (2)
V (Å3) 1142.9 (2) References
Z 4
Radiation type Mo K Brandenburg, K. & Putz, H. (2001). DIAMOND. Crystal Impact
(mm1) 5.26 GbR, Bonn, Germany.
Crystal size (mm) 0.28 0.22 0.18 Brown, I. D. & Altermatt, D. (1985). Acta Cryst. B41, 244–247.
Duisenberg, A. J. M. (1992). J. Appl. Cryst. 25, 92–96.
Data collection Efremov, V. A., Velikodnyi, Yu. A. & Trunov, V. K. (1975).
Diffractometer Enraf–Nonius CAD-4 Kristallografiya, 20, 287–292.
Absorption correction scan (North et al., 1968) Ennajeh, I., Georges, S., Smida, Y. B., Guesmi, A., Zid, M. F. &
Tmin, Tmax 0.224, 0.387
No. of measured, independent and 2678, 1238, 1208
Boughazala, H. (2015). RSC Adv. 5, 38918–38925.
observed [I > 2(I)] reflections Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854.
Rint 0.030 Fisher, D. (1955). Am. Mineral. 40, 1100–1109.
(sin /)max (Å1) 0.638 Harms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg,
Germany.
Refinement Khorari, S., Rulmont, A. & Tarte, P. (1997). J. Solid State Chem. 134,
R[F 2 > 2(F 2)], wR(F 2), S 0.023, 0.058, 1.17 31–37.
No. of reflections 1238 Klevtsova, R. F., Borisov, S. V., Bliznyuk, N. A., Glinskaya, L. A. &
No. of parameters 104 Klevtsov, P. V. (1991). Zh. Strukt. Khim. 32, 127–136.
max, min (e Å3) 0.80, 0.72
Klevtsova, R. F., Kozeeva, L. P. & Klevtsov, P. V. (1975).
Computer programs: CAD-4 EXPRESS (Duisenberg, 1992), XCAD4 (Harms & Kristallografiya, 20, 925–930.
Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), SHELXL2014 (Sheldrick, 2015), Laügt, M., Tordjman, I., Guitel, J. C. & Bassi, G. (1972). Acta Cryst.
DIAMOND (Brandenburg & Putz, 2001), WinGX (Farrugia, 2012) and publCIF B28, 2721–2725.
(Westrip, 2010). Menard, M. C., Ishii, R., Nakatsuji, S. & Chan, J. Y. (2011). Inorg.
Chem. 50, 8767–8773.
Moore, P. B. (1971). Am. Mineral. 56, 1955–1975.
milled in an agate mortar, placed in a porcelain crucible and Muessig, E., Bramnik, K. G. & Ehrenberg, H. (2003). Acta Cryst. B59,
611–616.
then preheated slowly in air at 623 K for 24 h, in order to Nasri, R., Fakhar Bourguiba, N., Zid, M. F. & Driss, A. (2014). Acta
eliminate volatile products. Thereafter, it was heated to a Cryst. E70, i47–i48.
temperature close to that of the fusion at 873 K. It was left at Nespolo, M. (2015). CHARDI-IT. Laboratoire CRM2, Université de
this temperature for 20 d to induce nucleation and crystal Nancy I, France.
growth. The final residue was first cooled slowly (5 K per half Nespolo, M. (2016). Acta Cryst. B72, 51–66.
North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst.
day) to 823 K and then rapidly (50 K h1) to room tempera- A24, 351–359.
ture. Green crystals of sufficient size for the measurement of Pauling, L. J. (1929). J. Am. Chem. Soc. 51, 1010–1026.
intensities were obtained. Reddy, M. V., Subba Rao, G. V. & Chowdari, B. V. R. (2013). Chem.
Rev. 113, 5364–5457.
Savina, A. A., Solodovnikov, S. F., Belov, D. A., Basovich, O. M.,
4. Refinement Solodovnikova, Z. A., Belov, D. A., Basovich, O. M., Solodovni-
kova, Z. A., Pokholok, K. V., Stefanovich, S. Y., Lazoryak, B. I. &
Crystal data, data collection and structure refinement details Khaikina, E. G. (2014). J. Solid State Chem. 220, 217–220.
are summarized in Table 3. We used of EADP and EXYZ Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
constraints within SHELXL2014 (Sheldrick, 2015) for Cu1/ Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8.
Na1 located at the same crystallographic site. Atom O4 was Shi, P. L., Xia, Z. G., Molokeev, M. S. & Atuchin, V. V. (2014). Dalton
Trans. 43, 9669–9676.
split over two sites (O4 and O41) as this displayed a very Solodovnikov, S. F., Klevtsov, P. V., Solodovnikova, Z. A., Glinskaya,
elongated displacement ellipsoid. The occupancies of O4 and L. A. & Klevtsova, R. F. (1998). J. Struct. Chem. 39, 230–237.
O41 were set to 0.5 in line with the occupany of Mo2; the two Solodovnikov, S. F. & Solodovnikova, Z. A. (1997). J. Struct. Chem.
separate O-atom sites (O4 and O41) correspond to two 38, 765–220.
different orientations of the Mo2O4 tetrahedron related by Tsyrenova, G. D., Solodovnikov, S. F., Pavlova, E. T., Khaikina, E. G.
& Solodovnikova, Z. A. (2009). Russ. J. Inorg. Chem. 54, 743–750.
symmetry. Refining atomic occupancies leads to a value of Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925.
0.497 (4) for the Cu atom. For conditions of electrical Xia, J., Song, L. X., Liu, W., Teng, Y., Wang, Q. S., Zhao, L. & Ruanb,
neutrality, we set the occupancy of the Cu atom as 0.5. This M. M. (2015). RSC Adv. 5, 12015–12024.
Acta Cryst. (2016). E72, 1103–1107 Dridi and Zid Na4Cu(MoO4)3 1107
supporting information
Acta Cryst. (2016). E72, 1103-1107 [https://doi.org/10.1107/S2056989016010367]
Synthesis, crystal structure and charge-distribution validation of β-

Na4Cu(MoO4)3 adopting the alluadite structure-type
Wassim Dridi and Mohamed Faouzi Zid
Computing details
Data collection: CAD-4 EXPRESS (Duisenberg, 1992); cell refinement: CAD-4 EXPRESS (Duisenberg, 1992); data
reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008);
program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: DIAMOND (Brandenburg &
Putz, 2001); software used to prepare material for publication: WinGX (Farrugia, 2012) and publCIF (Westrip, 2010).
Tetrasodium copper(II) tris[molybdate(VI)]
Crystal data
Na4Cu(MoO4)3 F(000) = 1180
Mr = 635.32 Dx = 3.692 Mg m−3
Monoclinic, C2/c Mo Kα radiation, λ = 0.71073 Å
a = 12.5318 (9) Å Cell parameters from 25 reflections
b = 13.8181 (9) Å θ = 10–15°
c = 7.1159 (7) Å µ = 5.26 mm−1
β = 111.95 (2)° T = 298 K
V = 1142.9 (2) Å3 Prism, green
Z=4 0.28 × 0.22 × 0.18 mm
Data collection
Enraf–Nonius CAD-4 1238 independent reflections
diffractometer 1208 reflections with I > 2σ(I)
ω/2θ scans Rint = 0.030
Absorption correction: ψ scan θmax = 27.0°, θmin = 2.3°
(North et al., 1968) h = −15→15
Tmin = 0.224, Tmax = 0.387 k = −1→17
2678 measured reflections l = −9→9
Refinement
Refinement on F2 w = 1/[σ2(Fo2) + (0.0173P)2 + 5.2182P]
Least-squares matrix: full where P = (Fo2 + 2Fc2)/3
R[F2 > 2σ(F2)] = 0.023 (Δ/σ)max = 0.001
wR(F2) = 0.058 Δρmax = 0.80 e Å−3
S = 1.17 Δρmin = −0.72 e Å−3
1238 reflections Extinction correction: SHELXL2014
104 parameters (Sheldrick, 2015),
0 restraints Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Extinction coefficient: 0.00081 (11)
Acta Cryst. (2016). E72, 1103-1107 sup-1

Special details
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance
matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles;
correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate
(isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
x y z Uiso*/Ueq Occ. (<1)

Mo1 0.72812 (2) 0.10879 (2) 0.11920 (4) 0.01991 (12)
Mo2 0.48085 (7) 0.28610 (4) 0.2400 (3) 0.0133 (3) 0.5
Cu1 0.70643 (5) 0.16100 (5) 0.61691 (9) 0.01741 (16) 0.5
Na1 0.70643 (5) 0.16100 (5) 0.61691 (9) 0.01741 (16) 0.5
Na2 0.5000 0.0169 (3) 0.2500 0.0482 (8)
Na3 0.0000 0.0000 0.0000 0.0299 (5)
Na4 0.5000 0.26934 (16) 0.7500 0.0219 (4)
O1 0.8745 (2) 0.0849 (2) 0.1859 (4) 0.0292 (6)
O2 0.6715 (2) 0.1702 (2) 0.8852 (4) 0.0337 (6)
O3 0.5390 (2) 0.2147 (2) 0.4714 (4) 0.0247 (6)
O4 0.3657 (5) 0.3629 (6) 0.2376 (11) 0.0239 (10) 0.5
O41 0.4153 (5) 0.3707 (6) 0.2551 (11) 0.0239 (10) 0.5
O5 0.6504 (3) −0.0001 (2) 0.0904 (5) 0.0346 (7)
O6 0.7095 (3) 0.1754 (2) 0.3178 (5) 0.0373 (7)
Atomic displacement parameters (Å2)
U11 U22 U33 U12 U13 U23

Mo1 0.01593 (17) 0.02069 (18) 0.01973 (18) 0.00034 (10) 0.00275 (11) −0.00104 (11)
Mo2 0.0147 (8) 0.0162 (2) 0.0079 (4) 0.0004 (2) 0.0032 (6) 0.0000 (3)
Cu1 0.0227 (3) 0.0219 (3) 0.0093 (3) −0.0007 (3) 0.0079 (2) 0.0006 (2)
Na1 0.0227 (3) 0.0219 (3) 0.0093 (3) −0.0007 (3) 0.0079 (2) 0.0006 (2)
Na2 0.0217 (11) 0.098 (3) 0.0203 (11) 0.000 0.0031 (9) 0.000
Na3 0.0397 (12) 0.0224 (10) 0.0179 (9) −0.0013 (10) −0.0004 (9) −0.0006 (9)
Na4 0.0225 (9) 0.0270 (11) 0.0189 (9) 0.000 0.0110 (7) 0.000
O1 0.0187 (12) 0.0341 (15) 0.0307 (14) 0.0037 (11) 0.0044 (10) 0.0072 (12)
O2 0.0268 (14) 0.0330 (16) 0.0327 (15) 0.0083 (12) 0.0011 (12) 0.0017 (13)
O3 0.0275 (13) 0.0335 (15) 0.0160 (12) −0.0003 (12) 0.0113 (10) 0.0011 (11)
O4 0.017 (3) 0.0250 (18) 0.0238 (18) 0.005 (3) 0.001 (3) −0.0039 (16)
O41 0.017 (3) 0.0250 (18) 0.0238 (18) 0.005 (3) 0.001 (3) −0.0039 (16)
O5 0.0357 (15) 0.0279 (14) 0.0410 (17) −0.0059 (13) 0.0152 (13) 0.0005 (13)
O6 0.0305 (14) 0.0398 (17) 0.0385 (17) 0.0010 (14) 0.0095 (13) −0.0084 (14)
Geometric parameters (Å, º)
Mo1—O1 1.746 (3) Na2—O5iv 2.462 (3)

Mo1—O5 1.762 (3) Na2—O5 2.549 (3)
Mo1—O2i 1.764 (3) Na2—O5ii 2.549 (3)
Mo1—O6 1.774 (3) Na3—O41vii 2.443 (7)
Acta Cryst. (2016). E72, 1103-1107 sup-2

Mo2—Mo2ii 0.447 (2) Na3—O41viii 2.443 (7)
Mo2—O41 1.456 (7) Na3—O1ix 2.493 (3)
Mo2—O3ii 1.738 (3) Na3—O1ii 2.493 (3)
Mo2—O41ii 1.740 (7) Na3—O1vi 2.675 (3)
Mo2—O4 1.787 (7) Na3—O1x 2.675 (3)
Mo2—O3 1.822 (3) Na3—O4vii 2.749 (7)
Mo2—O4ii 2.150 (6) Na3—O4viii 2.749 (7)
Cu1—O4iii 1.884 (6) Na3—O41xi 3.008 (7)
Cu1—O3 2.098 (3) Na3—O41xii 3.008 (7)
Cu1—O2 2.116 (3) Na4—O3 2.337 (2)
Cu1—O6 2.152 (3) Na4—O3xiii 2.337 (2)
Cu1—O5iv 2.317 (3) Na4—O2 2.424 (3)
Cu1—O6v 2.464 (4) Na4—O2xiii 2.424 (3)
Cu1—O41iii 2.467 (4) Na4—O1v 2.490 (4)
Na2—O5vi 2.462 (3) Na4—O1xiv 2.490 (4)
O1—Mo1—O5 110.42 (15) O3—Cu1—O2 85.28 (10)

O1—Mo1—O2i 111.01 (14) O4iii—Cu1—O6 93.4 (2)
O5—Mo1—O2i 106.95 (15) O3—Cu1—O6 82.16 (11)
O1—Mo1—O6 108.63 (14) O2—Cu1—O6 166.61 (12)
O5—Mo1—O6 107.69 (15) O4iii—Cu1—O5iv 96.1 (2)
O2i—Mo1—O6 112.08 (15) O3—Cu1—O5iv 94.73 (11)
O3ii—Mo2—O4 118.4 (2) O2—Cu1—O5iv 88.43 (12)
O3ii—Mo2—O3 110.75 (17) O6—Cu1—O5iv 97.18 (12)
O4—Mo2—O3 112.3 (3) O6v—Cu1—O2 89.55 (14)
O3ii—Mo2—O4ii 100.3 (2) O6v—Cu1—O4iii 76.78 (15)
O4—Mo2—O4ii 113.9 (4) O6v—Cu1—O5iv 172.13 (15)
O3—Mo2—O4ii 99.0 (2) O6v—Cu1—O6 86.42 (14)
O4iii—Cu1—O3 168.8 (2) O6v—Cu1—O3 92.66 (12)
O4iii—Cu1—O2 98.1 (2)
Symmetry codes: (i) x, y, z−1; (ii) −x+1, y, −z+1/2; (iii) x+1/2, −y+1/2, z+1/2; (iv) x, −y, z+1/2; (v) −x+3/2, −y+1/2, −z+1; (vi) −x+1, −y, −z; (vii) x−1/2,
−y+1/2, z−1/2; (viii) −x+1/2, y−1/2, −z+1/2; (ix) x−1, −y, z−1/2; (x) x−1, y, z; (xi) −x+1/2, −y+1/2, −z; (xii) x−1/2, y−1/2, z; (xiii) −x+1, y, −z+3/2; (xiv)
x−1/2, −y+1/2, z+1/2.
Acta Cryst. (2016). E72, 1103-1107 sup-3

Synthèse et étude structurale de Na9Cr(MoO4)6
Wassim Dridi, Ines Ennajeh* et Mohamed Faouzi Zid

ISSN 2056-9890
Laboratoire de Matériaux et Cristallochimie, Faculté des Sciences de Tunis, Université de Tunis El Manar, 2092 El Manar
Tunis, Tunisia. *Correspondence e-mail: inesnajeh@gmail.com
Reçu le 4 mars 2015 The title compound, nonasodium chromium(III) hexakis[molybdate(VI)],

Accepté le 24 mars 2015 Na9Cr(MoO4)6 was prepared by solid-state reactions. The basic structure units
are isolated polyhedral clusters composed of a central CrO6 octahedron sharing
vertices with six MoO4 tetrahedra to form an open framework in which the Na+
Édité par P. Roussel, ENSCL, France
cations are bound to the free vertices of the MoO4 tetrahedra. The Cr3+ cation
† has site symmetry of 32 (6a), one Na atom sits on a twofold axis (18e), and all
other atoms are at general positions. The bond-valance-sum model confirms the
expected values of ion charges. The title compound is isotypic with
Na9Sc(MoO4)6 and Na9Fe(MoO4)6. It is compared and discussed with similar
structures.
Keywords: crystal structure; molybdate(VI);
CrO6 octahedron; quaternary systems; open
framework
1. Contexte chimique
CCDC reference: 1055835 Ces dernières années, plusieurs équipes de recherche s’intér-
Supporting information: this article has essent à l’étude des systèmes quaternaires de type A–M–Mo–
supporting information at journals.iucr.org/e
O (A = cation monovalent et M = métal de transition). Les
molybdates présentent plusieurs domaines d’applications:
matériaux laser (Khal’baeva et al., 2013; Hanuza & Maczka,
1994), ferroélectriques (Isupov, 2005; Khal’baeva et al., 2012),
piézoélectriques, catalyseurs pour la synthése organique,
superionique, liants à haute température, matrices pour la
fixation des isotopes à vie longue et autres matériaux (Kotova
& Kozhevnikova, 2003).
Il est nécessaire de noter que les phases rhomboédriques
ont un intérêt particulier car elles présentent une cris-
Figure 1
Représentation des polyédres de coordination de l’unité structurale dans
Na9Cr(MoO4)6. Les éllipsoı̈des ont été définis avec 50% de probabilité.
[Codes de symétrie: (i) x + 23, x + y + 13, z + 56; (ii) y + 43, x + 23, z 56;
(iii) y 13, x + 13, z + 56; (iv) y 13, x + 13, z + 116; (v) y + 1, x y + 1, z; (vi)
x + y, x + 1, z; (vii) x y + 23, y + 43, z + 116; (viii) x + 23, x + y + 13,
z + 116.]
Acta Cryst. (2015). E71, 435–439 doi:10.1107/S2056989015005976 435

Figure 2
(a) Projection d’un cluster [Cr(MoO4)6]9, (b) représentation des unités structurales de Na9Cr(MoO4)6, (c) projection de la structure de Na9Cr(MoO4)6
dans le plan (001).
tallochimie similaire avec des composés du type NASICON, assurée par les cations Na+ (Fig. 1). Dans la charpente
qui sont caractérisés par des propriétés superioniques (Kotova anionique chaque octaèdre CrO6 partage ses six sommets avec
& Kozhevnikova, 2003). C’est dans ce cadre, que nous avons six tétraèdres MoO4 différents pour conduire aux clusters
choisi l’exploration des systèmes quaternaires, très peu étudiés [Cr(MoO4)6]9 (Fig. 2a). Ces derniers, dirigés selon [001],
à notre connaissance, A–Cr–Mo–O (A = ion monovalent). prennent une disposition laissant libre des espaces où résident
Une nouvelle phase de formulation Na9Cr(MoO4)6 a été les cations Na+ (Fig. 2b). La répartition de l’ensemble de ces
obtenue par réaction à l’état solide à 798 K. unités selon les trois directions de l’espace engendre une
charpente anionique zérodimensionnelle (0D) dans laquelle
les cations Na+ sont orientés vers les sommets libres des
2. Commentaire structurelle tétraèdres MoO4 (Fig. 2c).
L’unité structurale dans la phase Na9Cr(MoO4)6 est construite L’examen des facteurs géométriques révèle que les
à partir d’un octaèdre CrO6 relié par mise en commun d’un distances Mo—O et Cr—O dans respectivement les tétraèdres
sommet à un tétraèdre MoO4. La compensation de charges est MoO4 et les octaèdres CrO6 sont similaires à celles rencon-
trées dans la littérature (Sarapulova et al., 2009; Tsyrenova et
al., 2009; Gicquel-Mayer et al., 1981; Bensaid et al., 2013;
Averbuch-Pouchot et al., 1981). En effet, dans le tétraèdre
MoO4 les distances Mo—O sont situées dans la gamme
1,723 (4)–1,793 (4) Å. La plus longue liaison Mo—O corres-
pond à l’oxygène du pont mixte Cr–O1–Mo. Les distances
Cr—O sont toutes égales à 1,966 (3) Å (tableau 1). Les angles
O—Mo—O, situés entre 108,2 (2)—111,8 (2) correspondent à
des tétraèdres MoO4 presque réguliers.
Tableau 1
Longueurs des liaisons sélectionnées (Å).
Mo1—O4i 1.723 (4) Na1—O4 2.649 (4)
Mo1—O2 1.730 (4) Na2—O2 2.308 (4)
Mo1—O3ii 1.745 (4) Na2—O2iv 2.384 (5)
Mo1—O1iii 1.793 (4) Na2—O4v 2.414 (5)
Cr1—O1 1.966 (3) Na2—O3vi 2.473 (5)
Na1—O1 2.364 (4) Na2—O3v 2.559 (4)
Na1—O3 2.407 (4) Na2—O4vi 2.989 (5)
Figure 3 Symmetry codes: (i) x þ 23; x þ y þ 13; z þ 56; (ii) y þ 43; x þ 23; z 56; (iii)
Représentation d’un ruban mettant en évidence la connection entre les y 13; x þ 13; z þ 56; (iv) x y þ 23; x þ 13; z þ 13; (v) x þ y; y; z 12; (vi)
unités [Fe(MoO4)6] de la structure de Rb3FeMo4O15. y; x þ y; z þ 1.
436 Dridi et al. Na9Cr(MoO4)6 Acta Cryst. (2015). E71, 435–439

Figure 4
Projection de la structure de Rb3FeMo4O15 selon a. Figure 5
Présentation, selon [001], du réseau tridimensionnel du composé
Na3,5Cr1,83(AsO4)3.
De plus, le calcul des sommes de valences de liaison (BVS),
utilisant la formule empirique de Brown (2002) conduit aux
valeurs des charges des ions suivants: Mo1 (6,166), Cr1 en résulte, des rubans disposés parallèlement à la direction
(3,119), Na1 (1,021), Na2 (0,986) ce qui confirme les degrés [100] qui présente à leur tour une charpente unidimen-
d’oxydation des différents ions existant dans la phase étudiée. sionnelle possédant des espaces inter-rubans où résident les
Un examen bibliographique montre que le matériau obtenu cations monovalents Rb+ (Fig. 4). Un examen de la charpente
est isostructural aux composés ayant une formulation anionique du composé Na3,5Cr1,83(AsO4)3 révèle la présence
analogue Na9Sc(MoO4)6 (Savina, Solodovnikov et al., 2013) et des unités formulaires [Cr4(AsO4)6]6. En effet, elles sont
Na9Fe(MoO4)6 (Savina, Morozov et al., 2013). C’est deux formées par des unités [Cr1(AsO4)6] similaires à celles de
derniers cristallisent dans le même système rhomboédrique notre phase mais dans laquelle chaque octaèdre central Cr1O6
mais présentent une symétrie plus réduite groupe R3. En effet, est lié, en plus de partage d’arêtes, à respectivement trois
ils possèdent une unité asymétrique différente de celle de octaèdres CrO6 différents. Ces unités se connectent moyen-
notre composé. Elle est construite à partir de trois atomes de nant des ponts mixtes de type As–O–Cr formant ainsi un
sodium et d’un octaèdre MO6 (M = Sc, Fe) qui est relié par réseau tridimensionnel (Fig. 5). La charpente anionique du
mise en commun des sommets à deux tétraèdres MoO4 composé Na3Cr2(PO4)3 présente des unités de type
différents. La jonction de ces unités par partage de sommets [Cr(PO4)6]15 possédant une disposition de polyèdres simi-
conduit à une charpente similaire à celle du composé obtenu. laire à celle de notre phase. Dans le phosphate Na3Cr2(PO4)3,
chaque unité se lie par formation de ponts mixtes P–O–Cr
avec les unités voisines pour conduire à une charpente tridi-
3. Enquête de base de données mensionnelle (Fig. 6).
La comparaison de la structure de Na9Cr(MoO4)6 avec celles
rencontrées dans la littérature montre une certaine analogie
avec les composés Rb3FeMo4O15 qui cristallise dans le 4. Synthèse et cristallisation
système monoclinique groupe d’espace P21/c (Khal’baeva et Les cristaux relatifs à Na9Cr(MoO4)6 ont été obtenus par
al., 2010), Na3,5Cr1,83(AsO4)3 (Fakhar Bourguiba et al., 2013) réaction à l’état solide à partir des réactifs: Na2CO3
et Na3Cr2(PO4)3 (Genkina et al., 1991) cristallisant dans le (PROLABO, 70128, 99,6%), Cr(NO3)39H2O (FLUKA,
même groupe d’espace R3c. Le composé Rb3FeMo4O15 est 60832, 99,0%) et (NH4)6Mo7O244H2O (SIGMA-ALDRICH,
formé par des clusters [Fe(MoO4)6]9 ayant le même 13301, 99,0%) pris dans les proportions telques Na:Cr:Mo =
arrangement des polyèdres que celui du cluster 9:0,5:6. Après un broyage effectué dans un mortier en agate, le
[Cr(MoO4)6]9 existant dans notre structure. De plus, dans mélange a été mis dans un creuset en porcelaine, puis
Rb3Fe(MoO4)2Mo2O7, les deux clusters sont liés à l’aide d’une préchauffé à l’air à 453 K pendant 24 heures en vue d’éliminer
unité linéaire FeMo2O12 moyennant des ponts mixtes de type les composés volatils. Il est ensuite porté jusqu’à une
Mo–O–Fe et aussi des ponts simples Mo–O–Mo faisant température voisine de celle de la fusion à 798 K. Le mélange
apparaı̂tre des groupements dimolybdates Mo2O7 (Fig. 3). Il est abandonné à cette température pendant quelques jours
Acta Cryst. (2015). E71, 435–439 Dridi et al. Na9Cr(MoO4)6 437

Tableau 2
Détails expérimentaux.
Données crystallines
Formule chimique Na9Cr(MoO4)6
Mr 1218,55
Système cristallin, groupe d’espace Trigonal, R3c
Température (K) 298
a, c (Å) 14,707 (5), 19,175 (7)
V (Å3) 3592 (2)
Z 6
Type de rayonnement Mo K
(mm1) 3,74
Taille des cristaux (mm) 0,22 0,16 0,10
Collection de données
Diffractomètre Enraf–Nonius CAD-4
Correction d’absorption scan (North et al., 1968)
Tmin, Tmax 0,481, 0,676
Nombre de réflexions mesurées, 2549, 875, 678
indépendantes et observées
[I > 2(I)]
Rint 0,065
(sin /)max (Å1) 0,638
Affinement
R[F 2 > 2(F 2)], wR(F 2), S 0,028, 0,078, 1,13
Nombre de réflexions 875
Nombre de paramètres 63
max, min (e Å3) 0,60, 0,57
Figure 6 Programmes informatiques: CAD-4 EXPRESS (Duisenberg, 1992; Macı́ček & Yordanov,
Projection, selon c, de la structure du Na3Cr2(PO4)3. 1992), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 et SHELXL97 (Sheldrick, 2008),
DIAMOND (Brandenburg & Putz, 1999) et WinGX (Farrugia, 2012).
pour favoriser la germination et la croissance des cristaux. Par

la suite, il a subi en premier lieu un refroidissement lent (5 /
En effet, la structure a été résolue et affinée, sans ambiguı̈té
demi journée) jusqu’à 748 K puis rapide (50 /h) jusqu’à la
dans le groupe d’espace R3c par les méthodes directes utilis-
température ambiante. Des cristaux de couleur rouge de taille
ant la chaı́ne de programmes SHELXS97 (Sheldrick, 2008)
suffisante pour les mesures des intensités sont obtenus. La
inclue dans le système WinGX publication (Farrugia, 2012),
morphologie et l’analyse élementaire, ont été faites au moyent
partant de la formule Na3Cr1Mo3O12. Les premiers cycles
d’un microscope électronique à balayage de type FEI
d’affinements ont permis de localiser la plupart des atomes.
QUANTA 200. Cette analyse confirme la présence des
Un examen de la Fourier différence et en se basant sur des
éléments attendus: Na, Cr, Mo et l’oxyène (Fig. 7).
considérations géométriques et de neutralité électrique, l’un
des atomes d’oxygène a été remplacé par un sodium. L’af-
finement de tous les paramètres variables conduit à des
5. Affinement
ellipsoı̈des bien définis. Les densités d’électrons maximum et
Les conditions expérimentales de la collecte des données et le minimum restants dans la Fourier-différence finale sont
résultat final de l’affinement sont rassemblés dans le tableau 2. acceptables et sont situées respectivement à 0,70 Å de O4 et à
1,06 Å de Mo1.
Remerciements
Les auteurs remercient le Ministère de l’Enseignement
Supérieur, de la Recherche Scientifique et de la Technologie
de la Tunisie pour le financement du laboratoire LMC (code
LR01ES11).
Références
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Bensaid, H., El Bouari, A., Benmokhtar, S., Manoun, B., Bih, L. &
Lazor, P. (2013). J. Mol. Struct. 1031, 152–159.
Figure 7 Brandenburg, K. & Putz, H. (1999). DIAMOND. Crystal Impact
Morphologie et analyse qualitative d’un cristal de Na9Cr(MoO4)6. GbR, Bonn, Allemagne.
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Brown, I. D. (2002). The Chemical Bond in Inorganic Chemistry. The Khal’baeva, K. M., Solodovnikov, S. F., Khaikina, E. G., Kadyrova,
Bond Valence Model. Oxford University Press. Y. M., Solodovnikova, Z. A. & Basovich, O. M. (2013). J. Solid State
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Harms, K. & Wocadlo, S. (1995). XCAD4. Université de Marburg, Lazoryak, B. I. (2013). Acta Cryst. C69, 1301–1303.
Allemagne. Savina, A. A. F., Solodovnikov, S. M., Basovich, O. A., Solodovni-
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Khal’baeva, K. M., Solodovnikov, S. F., Khaikina, E. G., Kadyrova, Stefanovich, S. Y. I., Lazoryak, B. & Khaikina, E. G. (2013). J.
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Acta Cryst. (2015). E71, 435–439 Dridi et al. Na9Cr(MoO4)6 439

Acta Cryst. (2015). E71, 435-439 [https://doi.org/10.1107/S2056989015005976]
Synthèse et étude structurale de Na9Cr(MoO4)6

Wassim Dridi, Ines Ennajeh et Mohamed Faouzi Zid
Computing details
Data collection: CAD-4 EXPRESS (Duisenberg, 1992; Macíček & Yordanov, 1992); cell refinement: CAD-4 EXPRESS
(Duisenberg, 1992; Macíček & Yordanov, 1992); data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to
solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008);
molecular graphics: DIAMOND (Brandenburg & Putz, 1999); software used to prepare material for publication: WinGX
(Farrugia, 2012).
Nonasodium chromium(III) hexakis[molybdate(VI)]
Crystal data
Na9Cr(MoO4)6 Dx = 3.380 Mg m−3
Mr = 1218.55 Mo Kα radiation, λ = 0.71073 Å
Trigonal, R3c Cell parameters from 25 reflections
Hall symbol: -R 3 2"c θ = 10–15°
a = 14.707 (5) Å µ = 3.74 mm−1
c = 19.175 (7) Å T = 298 K
V = 3592 (2) Å3 Prism, red
Z=6 0.22 × 0.16 × 0.10 mm
F(000) = 3402
Data collection
Enraf–Nonius CAD-4 875 independent reflections
diffractometer 678 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube Rint = 0.065
Graphite monochromator θmax = 27.0°, θmin = 2.7°
ω/2θ scans h = −16→4
Absorption correction: ψ scan k = −17→1
(North et al., 1968) l = −24→24
Tmin = 0.481, Tmax = 0.676 2 standard reflections every 2 reflections
2549 measured reflections intensity decay: 1.2%
Refinement
Refinement on F2 Secondary atom site location: difference Fourier
Least-squares matrix: full map
R[F2 > 2σ(F2)] = 0.028 w = 1/[σ2(Fo2) + (0.0286P)2 + 21.2743P]
wR(F2) = 0.078 where P = (Fo2 + 2Fc2)/3
S = 1.13 (Δ/σ)max < 0.001
875 reflections Δρmax = 0.60 e Å−3
63 parameters Δρmin = −0.57 e Å−3
0 restraints Extinction correction: SHELXL,
Primary atom site location: structure-invariant Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
direct methods Extinction coefficient: 0.00013 (4)
Acta Cryst. (2015). E71, 435-439 sup-1

Special details
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full
covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and
torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry.
An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2,
conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used
only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2
are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
x y z Uiso*/Ueq
Mo1 0.51969 (4) 0.66053 (4) 0.02393 (2) 0.01759 (19)
Cr1 0.3333 0.6667 0.9167 0.0096 (4)
Na1 0.1089 (2) 0.6667 0.9167 0.0285 (8)
Na2 0.5617 (2) 0.6706 (2) 0.21706 (11) 0.0334 (6)
O1 0.2729 (3) 0.7346 (3) 0.85988 (19) 0.0177 (8)
O2 0.4881 (4) 0.6129 (4) 0.1082 (2) 0.0342 (11)
O3 0.0440 (4) 0.7277 (3) 0.8230 (2) 0.0267 (9)
O4 0.0834 (3) 0.5458 (4) 0.8075 (2) 0.0312 (10)
Atomic displacement parameters (Å2)
U11 U22 U33 U12 U13 U23

Mo1 0.0165 (3) 0.0218 (3) 0.0164 (3) 0.0110 (2) −0.00230 (17) 0.00171 (18)
Cr1 0.0070 (5) 0.0070 (5) 0.0149 (8) 0.0035 (3) 0.000 0.000
Na1 0.0211 (11) 0.049 (2) 0.0250 (15) 0.0244 (12) 0.0073 (8) 0.0146 (16)
Na2 0.0341 (14) 0.0518 (18) 0.0200 (11) 0.0258 (14) −0.0021 (10) −0.0027 (11)
O1 0.0142 (18) 0.0155 (19) 0.0246 (18) 0.0083 (15) −0.0003 (15) 0.0083 (15)
O2 0.037 (3) 0.041 (3) 0.0153 (18) 0.012 (2) −0.0028 (18) 0.0009 (19)
O3 0.037 (3) 0.024 (2) 0.028 (2) 0.0221 (19) −0.0003 (19) −0.0009 (19)
O4 0.025 (2) 0.031 (2) 0.043 (2) 0.018 (2) −0.0141 (19) −0.014 (2)
Geometric parameters (Å, º)
Mo1—O4i 1.723 (4) Na1—O1 2.364 (4)

Mo1—O2 1.730 (4) Na1—O3 2.407 (4)
Mo1—O3ii 1.745 (4) Na1—O3vii 2.407 (4)
Mo1—O1iii 1.793 (4) Na1—O4 2.649 (4)
Cr1—O1iv 1.966 (3) Na1—O4vii 2.649 (4)
Cr1—O1 1.966 (3) Na2—O2 2.308 (4)
Cr1—O1v 1.966 (3) Na2—O2ix 2.384 (5)
Cr1—O1vi 1.966 (3) Na2—O4x 2.414 (5)
Cr1—O1vii 1.966 (3) Na2—O3xi 2.473 (5)
Cr1—O1viii 1.966 (3) Na2—O3x 2.559 (4)
Na1—O1vii 2.364 (4) Na2—O4xi 2.989 (5)
O4i—Mo1—O2 109.2 (2) O3—Na1—O4vii 120.99 (15)
Acta Cryst. (2015). E71, 435-439 sup-2

O4i—Mo1—O3ii 108.3 (2) O3vii—Na1—O4vii 73.23 (14)
O2—Mo1—O3ii 108.2 (2) O4—Na1—O4vii 157.6 (2)
O4i—Mo1—O1iii 111.80 (18) O2—Na2—O2ix 98.5 (2)
O2—Mo1—O1iii 108.64 (19) O2—Na2—O4x 112.11 (19)
O3ii—Mo1—O1iii 110.60 (18) O2ix—Na2—O4x 110.62 (17)
O1iv—Cr1—O1 176.8 (2) O2—Na2—O3xi 90.60 (17)
O1iv—Cr1—O1v 90.1 (2) O2ix—Na2—O3xi 121.52 (18)
O1—Cr1—O1v 92.29 (15) O4x—Na2—O3xi 118.75 (17)
O1iv—Cr1—O1vi 85.4 (2) O2—Na2—O3x 164.06 (19)
O1—Cr1—O1vi 92.29 (15) O2ix—Na2—O3x 92.00 (17)
O1v—Cr1—O1vi 92.29 (15) O4x—Na2—O3x 74.78 (15)
O1iv—Cr1—O1vii 92.28 (15) O3xi—Na2—O3x 73.64 (17)
O1—Cr1—O1vii 90.1 (2) O2—Na2—O4xi 72.48 (16)
O1v—Cr1—O1vii 85.4 (2) O2ix—Na2—O4xi 168.70 (19)
O1vi—Cr1—O1vii 176.8 (2) O4x—Na2—O4xi 68.09 (17)
O1iv—Cr1—O1viii 92.28 (15) O3xi—Na2—O4xi 66.40 (14)
O1—Cr1—O1viii 85.4 (2) O3x—Na2—O4xi 98.30 (16)
O1v—Cr1—O1viii 176.8 (2) Mo1—O2—Na2 135.6 (3)
O1vi—Cr1—O1viii 90.1 (2) Mo1—O2—Na2xii 114.0 (2)
O1vii—Cr1—O1viii 92.28 (15) Na2—O2—Na2xii 110.28 (17)
O1vii—Na1—O1 72.09 (19) Mo1xiii—O3—Na1 108.60 (18)
O1vii—Na1—O3 158.89 (15) Mo1xiii—O3—Na2xiv 111.7 (2)
O1—Na1—O3 90.55 (13) Na1—O3—Na2xiv 101.42 (16)
O1vii—Na1—O3vii 90.55 (14) Mo1xiii—O3—Na2xv 147.5 (2)
O1—Na1—O3vii 158.89 (15) Na1—O3—Na2xv 100.80 (16)
O3—Na1—O3vii 108.7 (2) Na2xiv—O3—Na2xv 74.53 (16)
O1vii—Na1—O4 89.66 (15) Mo1i—O4—Na2xv 123.6 (2)
O1—Na1—O4 72.06 (14) Mo1i—O4—Na1 117.1 (2)
O3—Na1—O4 73.23 (14) Na2xv—O4—Na1 98.12 (17)
O3vii—Na1—O4 120.99 (15) Mo1i—O4—Na2xiv 151.0 (2)
O1vii—Na1—O4vii 72.06 (14) Na2xv—O4—Na2xiv 67.71 (15)
O1—Na1—O4vii 89.65 (15) Na1—O4—Na2xiv 83.91 (14)
Symmetry codes: (i) −x+2/3, −x+y+1/3, −z+5/6; (ii) −y+4/3, −x+2/3, z−5/6; (iii) y−1/3, x+1/3, −z+5/6; (iv) y−1/3, x+1/3, −z+11/6; (v) −y+1, x−y+1, z; (vi)
−x+y, −x+1, z; (vii) x−y+2/3, −y+4/3, −z+11/6; (viii) −x+2/3, −x+y+1/3, −z+11/6; (ix) x−y+2/3, x+1/3, −z+1/3; (x) −x+y, y, z−1/2; (xi) y, −x+y, −z+1; (xii)
y−1/3, −x+y+1/3, −z+1/3; (xiii) −y+2/3, −x+4/3, z+5/6; (xiv) x−y, x, −z+1; (xv) −x+y, y, z+1/2.
Acta Cryst. (2015). E71, 435-439 sup-3

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Journal of Alloys and Compounds 731 (2018) 955e963

Contents lists available at ScienceDirect

Journal of Alloys and Compounds

Characterization of a sodium molybdate compound b-Na4Cu(MoO4)3

1. Introduction importance in the current technology, especially in the context of

respect, a very exhaustive studies carried out by many scientists in

positions with the occupancies of 0.5. This compound adopts the

3.2. Complex impedance studies of b-Na4Cu(MoO4)3

Fig. 2 shows the Nyquist diagrams of b-Na4Cu(MoO4)3 in the

The values of ionic conductivities of b-Na4Cu(MoO4)3 are rep-

573 503570 2.1791011 1.0183107 7.0291011 1.0680107 Grains 573e693 1.36

Gacoustic ¼ 1Auþ 2Bu

Goptic ¼ 27Ag þ 27Bg þ 32Au þ 31Bu

All Ag and Bg modes are Raman-active whereas Au and Bu modes

Gn2 ¼ 2A(R) (R) (IR)

Gn3 ¼ 3A(R) (R) (IR)

Gn4 ¼ 3A(R) (R) (IR)

Where as 18 modes of the Mo2O4 unit at C2 sites are distributed as

GMo2O4 ¼ 5A(R) (R) (IR)

Gn1 ¼ A(R) (IR)

Gn2 ¼ 2A(R) (IR)

Gn3 ¼ Ag þ 2Bg þ Au þ2Bu

Gn4 ¼ Ag þ 2Bg þ Au þ2Bu

Regarding external modes of MoO4, they can be subdivided into

Gn1 ¼ A(R) (R) (IR)

Gtransl Mo2O4 ¼ Ag(R) þ 2Bg(R) þ Au(IR) þ2Bu(IR)

Glibration Mo1O4 ¼ 3A(R) (R) (IR)

Glibration Mo2O4 ¼ Ag(R) þ 2Bg(R) þ Au(IR) þ2Bu(IR)

The presence of an inversion center in the b-Na4Cu(MoO4)3

3.4. Optical studies

Fig. 6. Diffuse reﬂection spectrum of b-Na4Cu(MoO4)3.

The performed studies revealed that grain boundaries cause a

Synthesis, crystal structure and alkaline pathways simulation

Received: 3 March 2022 / Accepted: 2 December 2022

Molybdates constitute an important class of materials exhib-

determination of the pathways of N ­ a+ in N­ a4Co7(AsO4)7,

Table 2 Atomic coordinates Atom X y z Wyck Ueq (Å2) Occ. (< 1)

Symmetry codes: (i) − x + y + 1, − x + 1, z; (ii) − y + 1, x − y, z; (iii) y, − x + y, − z + 1; (iv) x − y + 1, x, − z + 1;

Fig. 3 Representation of the coordination polyhedra of

Table 5 Energy and atoms coordinate of equilibrium and interstitial

Na1 1 0.000 0.000 0.000 0.000

Fig. 4 Representation of the coordination polyhedra of

Fig. 6 Projection of the unit cell showing the equilibrium site of

from 2.87(3) Å to 3.12(9) Å, with an average distance of

Fig. 5 K1 and K2 cations environments Alkaline conduction pathways simulation

The simulation of the transport pathways of N ­ a+ and K

combinations to form an infinite pathway. The activation

The materials of A–M–X–O systems (A: alkaline, M = transi-

Table 7 Crystallographic data Formula System S.G Ea (eV)* Ref.

Fig. 9 Isosurfaces of alkaline

Vibrational and optical studies of ­Na0.45K1.55Cu3(MoO4)4

Received: 28 October 2019 / Accepted: 28 March 2020

Keywords Molybdate · Phonon properties · Raman spectra · IR spectra · Band gap

Introduction spaces, tunnels or cages. The type of adopted structure deter-

resolution. The laser power was set to 1 mW to avoid sample

Fig. 1 Experimental and

Table 1 Correlation table for N

(4e) ν2 E(R) 2A(R,IR) 2Ag + 2Bg + 2Au + 2B(IR)

Cu2+ (4e) T′ 3A(R,IR) 3A(R) (R) (IR) (IR)

determination of the pathways of N a+ in N a4Co7(AsO4)7,

The simulation of the transport pathways of N a+ and K

Vibrational and optical studies of Na0.45K1.55Cu3(MoO4)4

−Z㰀㰀 (105 Ohm)

occurring at different frequencies exhibit a single conduction mecha

K0.12Na0.54Ag0.34Nb4AsO13 compound synthesized via a solid state re