ARTICLE IN PRESS

Journal of Solid State Chemistry 177 (2004) 28412849

Synthesis, structure and magnetic properties of cobalt(II) and

copper(II) coordination polymers assembled by phthalate
and 4-methylimidazole
Svetlana G. Baca,a,* Stanislav T. Malinovskii,a Patrick Franz,b Christina Ambrus,b
Helen Stoeckli-Evans,c Nicolae Gerbeleu,a and Silvio Decurtinsb
a
Institute of Chemistry, Academy of Sciences of R. Moldova, Academiei 3, MD-2028 Chisinau, Moldova
b
Department of Chemistry and Biochemistry, University of Berne, CH-3012 Berne, Switzerland
c
Institut de Chimie, Universite de Neuchatel, CH-2007 Neuchatel, Switzerland
Received 31 March 2004; received in revised form 28 April 2004; accepted 2 May 2004

Abstract

New coordination polymers [M(Pht)(4-MeIm)2(H2O)]n (M=Co (1), Cu (2); Pht2
=dianion of o-phthalic acid; 4-MeIm=4-
methylimidazole) have been synthesized and characterized by IR spectroscopy, X-ray crystallography, thermogravimetric analysis
and magnetic measurements. The crystal structures of 1 and 2 are isostructural and consist of [M(4-MeIm)2(H2O)] building units
linked in innite 1D helical chains by 1,6-bridging phthalate ions which also act as chelating ligands through two O atoms from one
carboxylate group in the case of 1. In complex 1, each Co(II) atom adopts a distorted octahedral N2O4 geometry being coordinated
by two N atoms from two 4-MeIm, three O atoms of two phthalate residues and one O atom of a water molecule, whereas the
square-pyramidal N2O3 coordination of the Cu(II) atom in 2 includes two N atoms of N-containing ligands, two O atoms of two
carboxylate groups from different Pht, and a water molecule. An additional strong OH?O hydrogen bond between a carboxylate
group of the phthalate ligand and a coordinated water molecule join the 1D helical chains to form a 2D network in both
compounds. The thermal dependences of the magnetic susceptibilities of the polymeric helical Co(II) chain compound 1 were
simulated within the temperature range 20300 K as a single ion case, whereas for the Cu(II) compound 2, the simulations between
25 and 300 K, were made for a linear chain using the BonnerFisher approximation. Modelling the experimental data of compound
1 with MAGPACK resulted in: g 2:6; |D|=62 cm
1. Calculations using the BonnerFisher approximation gave the following
result for compound 2: g 2:18; J 20:4 cm
1.
r 2004 Elsevier Inc. All rights reserved.

Keywords: Phthalate compounds; Carboxylate complexes; Dicarboxylic acid; Cobalt(II); Copper(II); Coordination polymer; Crystal structure;
Helical chain; Magnetic properties

1. Introduction tures, but also due to their advantageous properties such

as bulk magnetic behavior, high dimensionality, optical
Inorganic coordination polymers or solid-state poly- activity and thermal stability. In particular, coordina-
mers have received considerable attention in the past few tion polymers with terephthalic [2], isophthalic [3] and
years due to possible applications as new materials in phthalic acids [431] have been extensively studied.
catalysis, adsorption, ion exchange, separation, mag- Among these isomeric forms the o-phthalate ligand,
netic devices, etc. (for recent reviews see [1]). Metal with two carboxylic groups in ortho-position, can adopt
coordination polymers containing dicarboxylate ions as the most diverse bonding modes (26 coordination modes
the organic spacer have been the subject of particular [32]) in metal complexes. As a result, it can be expected
interest not only because of their fascinating architec- that more complicated and unexpected architectures
leading to new properties and reactivity can be
*Corresponding author. Fax: +373-22-73-9611. constructed. We have recently become interested in the
E-mail address: sbaca md@yahoo.com (S.G. Baca). synthesis of 3d-coordination compounds with the

0022-4596/$ - see front matter r 2004 Elsevier Inc. All rights reserved.
doi:10.1016/j.jssc.2004.05.001
 ARTICLE IN PRESS
2842 S.G. Baca et al. / Journal of Solid State Chemistry 177 (2004) 28412849

phthalate and N-containing ligands. Copper(II) [3233], 817m, 767m, 722m, 701w, 657s, 621m, 561w. Single
cobalt(II) [32,34], and zinc(II) [32,3536] coordination crystals suitable for diffraction studies were obtained by
polymers have been reported so far. In an extension of recrystallization of 2 from hot aqueous solution.
the study here we report on the synthesis, crystal
structure and magnetic properties of new cobalt(II) 2.3. Crystal structure determination
and copper(II) mixed-ligand coordination polymers
[M(Pht)(4-MeIm)2(H2O)]n (where Pht2
=dianion of Single crystal X-ray diffraction data for 1 and 2 were
o-phthalic acid, 4-MeIm=4-methylimidazole). collected on a Stoe Mark IIImaging Plate Diffract-
ometer System [37] equipped with a two-circle goni-
ometer and using MoKa graphite-monochromated
2. Experimental radiation at 153 K. Image plate distance 100 mm, o
rotation scans 0180 at f 0 , and 035 at 90 , step
2.1. Materials and methods Do 1:2 ; 2y range 2.2959.53 , dmaxdmin=17.799
0.716 A. The crystallographic data and details on the
All the starting materials were reagent grade and used renements for 1 and 2 are summarized in Table 1. The
as purchased. The infrared spectra were recorded on a structures were solved by direct methods using the
PerkinElmer Spectrum One spectrometer using KBr programme SHELXS-97 [38]. The renement and all
pellets in the region 4000400 cm
1. Thermogravimetric further calculations were carried out using SHELXL-97
analyses were carried out in dry nitrogen (60 mL/min) at [39]. The H-atoms were located from Fourier difference
a heating rate of 5 C/min from room temperature (r.t.) maps and rened isotropically. The water molecule H-
to 600 C on a Mettler-Toledo TA 50 instrument. atoms were also located from difference maps but were
held xed with Uiso=1.5(UeqOatom) A2. The non-H
2.2. Synthesis atoms were rened anisotropically, using weighted full-
matrix least squares on F2. Selected bond lengths and
2.2.1. [Co(Pht)(4-MeIm)2(H2O)]n (1) angles for 1 and 2 are listed in Table 2. Crystallographic
A solution of Co(O2CMe)2  4H2O (1.24 g, 5 mmol) in data for the structural analysis have been deposited with
water (10 mL) was added to a hot solution of KHPht the Cambridge Crystallographic Data Centre, CCDC
(1.02 g, 5 mmol) and 4-MeIm (0.82 g, 10 mmol) in water nos. 234706 (1), 234707 (2). Copies of this information
(10 mL). The resulting mixture was stirred and heated may be obtained from The Director, CCDC, 12 Union
for 30 min and left to stand overnight at r.t. The dark Road, Cambridge, CB2 1EZ, UK (fax: +44-1233-
red crystalline product was ltered off, washed with 336033; e-mail: deposit@ccdc.cam.ac.uk or www:
water and ethanol and dried in air. Yield: 1 g, 50%. An http://www.ccdc.cam.ac.uk).
additional batch of 1 can be obtained by keeping the
mother ltrate in air over 2 weeks (yield ca. 20%). Anal. 2.4. Magnetic measurements
Calc. for C16H18CoN4O5: C, 47.42%; H, 4.48%; N,
13.82%. Found: C, 47.94%; H, 4.54%; N, 13.81%. IR Magnetic susceptibility data of powdered samples
data (KBr, cm
1): 3414s,br, 3211s, 3008sh, 1596sh, were collected on a MPMS Quantum Design SQUID
1559vs,br, 1493s, 1446s, 1417vs, 1396vs, 1259w, 1234w, magnetometer (XL-5) in the temperature range of 300
1158w, 1108m, 1088w, 962m, 870sh, 840m, 816m, 770m, 1.8 K and at a eld of 1000 G. The samples were placed
725m, 701m, 662s, 624w, 584m. Single crystals suitable in a gelatine capsule and a straw was used as the sample
for diffraction studies were obtained by recrystallization holder. The output data were corrected for the
of 1 from hot aqueous solution. experimentally determined diamagnetism of the sample
holder and the diamagnetism of the sample calculated
2.2.2. [Cu(Pht)(4-MeIm)2(H2O)]n (2) from Pascals constants. The LevenbergMarquardt
A solution of Cu(O2CMe)2  H2O (1 g, 5 mmol) in least-squares tting algorithm, in combination with
water (10 mL) was added to a warm solution of o- MAGPACK [40], was used to model the experimental
phthalic acid (0.83 g, 5 mmol) and 4-MeIm (0.82 g, magnetic susceptibility data.
10 mmol) in water (30 mL). The resulting mixture was
stirred and heated for 30 min. The blue microcrystalline
precipitate was ltered off, washed with water and 3. Results and discussion
ethanol and dried in air. Yield: 1.3 g, 64.2%. Anal. Calc.
for C16H18CuN4O5: C, 46.88%; H, 4.43%; N, 13.67%. 3.1. Synthesis and preliminary characterization
Found: C, 46.2%; H, 4.37%; N, 13.2%. IR data (KBr,
cm
1): 3430s,br, 3145br, 3004sh, 1604sh, 1584sh, Reaction of metal(II) acetate with 4-MeIm and
1552vs,br, 1502s, 1489s, 1446sh, 1434s, 1407vs, 1396vs, KHPht or H2Pht in water in a 1:2:1 mole ratio
1261w, 1238w, 1160w, 1110s, 1088w, 971m, 852m, under heating leads to formation of polymers
 ARTICLE IN PRESS
S.G. Baca et al. / Journal of Solid State Chemistry 177 (2004) 28412849 2843

Table 1
Crystal data and details of structural determinations

1 2

Empirical formula C16H18CoN4O5 C16H18CuN4O5

Formula weight 405.27 409.88
Temperature (K) 153(2) 153(2)
Wavelength (A) 0.71073 0.71073
Crystal size (mm) 0.40  0.40  0.40 0.40  0.20  0.15
Crystal system Monoclinic Monoclinic
Space group P21 =n P21 =n
a (A) 11.4507(9) 11.6836(15)
b (A) 9.1139(5) 9.0050(8)
c (A) 16.3485(12) 16.504(2)
b (deg) 100.178(6) 100.159(10)
V (A3) 1679.3(2) 1709.2(3)
Z 4 4
Dc (g/cm3) 1.603 1.593
m (mm
1) 1.059 1.314
F(000) 836 844
y range for data coll. (deg) 2.0129.53 1.9829.65
Index ranges
15php15,
14php16,

11pkp12,
12pkp10,

22plp22
22plp22

Reections measured 20538 20538

Independent reections 4647 [R(int)=0.0494] 4647[R(int)=0.0494]
Data/restraints/parameters 4647/0/300 4654/0/300
Goodness-of-t on F2 1.051 1.005
Final R indices [I42sI] R1 0:0284 R1 0:04212
wR2 0:0745 wR2 0:0936

R indices (all data) R1 0:0321 R1 0:0673

wR2 0:0763 wR2 0:1042

Largest diff. peak and hole (e/A3) 0.509 and
0.505 0.465 and
0.525

[M(Pht)(4-MeIm)2(H2O)]n (M=Co (1) and Cu (2)) in moieties of 2 started at lower temperature (ca. 180 C)
ca. 70% and 64% yields, respectively. The IR spectra of and was then followed by a two-step total weight loss of
these compounds exhibit very strong bands in the 1604 61.68% from 180 C to 300 C, which is due to the loss of
1552 and 14171396 cm
1 regions due to the asymmetric two molecules of 4-MeIm and one molecule of phenyl
and symmetric stretching vibrations of the coordinated radical [44] (calculated 58.63%). Further weight loss of
carboxylate groups of the phthalate ligand, respectively 13.53%, corresponding to the elimination of two
[4143]. The peaks that appeared at 32113145 cm
1 can molecules of CO [45] (calculated 13.67%), occurred
be attributed to the NH stretching vibration of 4- between 420 C and 530 C. The nal product is CuO
MeIm. The presence of coordinated water molecules in 1 with the remaining percentage of 20.28% (calculated
and 2 caused the appearance of broad absorption bands 19.40%).
with maxima at 3414 and 3430 cm
1, respectively.
Thermogravimetric analyses of the polymers performed 3.2. Crystal structures
in the range 25600 C indicate that these coordinated
water molecules are lost rst between 100190 C for 1 3.2.1. [Co(Pht)(4-MeIm)2(H2O)]n (1)
and 80150 C for 2. The weight losses of 4.59% and X-ray structural analysis reveals that 1 consists of
4.57%, respectively, are close to the theoretical values [Co(4-MeIm)2(H2O)] entities linked by bridging phtha-
(4.47% and 4.4%) for the removal of one water late anions into an innite polymeric helical chain (Fig.
molecule per formula unit. On further heating, 1 lost 1). Each cobalt atom in 1 has a distorted octahedral
weight between 200 C and 320 C corresponding to one (N2O4) coordination geometry with two nitrogen atoms
4-MeIm ligand (observed 18.18%, calculated 20.16%), N(1) and N(3) from two 4-MeIm moieties (Co(1)N(1)
then from 320 C to 520 C complex 1 decomposes 2.092(1), Co(1)N(3) 2.087(1) A), two oxygen
abruptly to give the oxide CoO (found 20.30%, atoms O(3a) and O(1w) belonging to the phthalate
calculated 18.49%). The decomposition of the organic moiety (Co(1)O(3a) 2.126(1) A) and a water molecule
 ARTICLE IN PRESS
2844 S.G. Baca et al. / Journal of Solid State Chemistry 177 (2004) 28412849

Table 2
Selected bond distances (A) and angles (deg)

1 2

Bond distances
Co(1)N(1) 2.092(1) Cu(1)N(1) 1.978(2)
Co(1)N(3) 2.087(1) Cu(1)N(3) 1.981(2)
Co(1)O(1w) 2.113(1) Cu(1)O(1w) 2.040(2)
Co(1)O(3a) 2.126(1) Cu(1)O(3a) 2.009(2)
Co(1)O(1) 2.129(1) Cu(1)O(1) 2.353(2)
Co(1)O(4a) 2.261(1) Cu(1)O(4a) 2.630(2)

Bond angles
N(3)Co(1)N(1) 177.18(4) N(3)Cu(1)N(1) 177.65(9)
N(3)Co(1)O(1w) 86.94(4) N(3)Cu(1)O(1w) 87.94(8)
N(1)Co(1)O(1w) 88.68(4) N(1)Cu(1)O(1w) 89.98(8)
N(3)Co(1)O(3a) 91.66(4) N(3)Cu(1)O(3a) 91.85(8)
N(1)Co(1)O(3a) 91.16(4) N(1)Cu(1)O(3a) 90.41(8)
O(1w)Co(1)O(3a) 169.98(4) O(1w)Cu(1)O(3a) 167.96(8)
N(3)Co(1)O(1) 88.64(4) N(3)Cu(1)O(1) 88.20(8)
N(1)Co(1)O(1) 91.10(4) N(1)Cu(1)O(1) 90.72(8)
O(1w)Co(1)O(1) 93.29(4) O(1w)Cu(1)O(1) 90.56(8)
O(3a)Co(1)O(1) 96.73(3) O(3a)Cu(1)O(1) 101.47(7)
N(3)Co(1)O(4a) 94.41(4)
N(1)Co(1)O(4a) 86.93(4)
O(1w)Co(1)O(4a) 110.04(4)
O(3a)Co(1)O(4a) 59.94(3)
O(1)Co(1)O(4a) 156.50(3)

Symmetry transformations used to generate equivalent atoms: a
x 1=2; y
1=2;
z 1=2:

the second Pht ligand (Co(1)O(1) 2.129(1) A). The Co

N distances are slightly shorter than CoO distances,
but all distances are comparable with those of other
Co(II) complexes, containing as co-ligands both carbox-
ylate and imidazole or its derivatives (CoN 2.013(1)
2.069(1) A and CoO 1.962(1)2.145(2) A [34,46,47]),
with the exception of the axial CoO(4a)carboxylate
distance, which is longer. The trans angles around the
Co center range from 156.50(3) to 177.18(4) , whereas
the cis angles range from 59.94(3) to 110.04(4) (Table
2). The main distortion from the octahedral geometry in
the coordination polyhedron is due to the small angle
O(3a)Co(1)O(4a) of 59.94(3) at the chelate carbox-
ylate group of the Pht ligand. This distortion is common
for carboxylate groups acting in the 1,3-chelating
manner and it was found, e.g., in [Cu(HPht)2Py2]
(58.00(1) ) and [Cu(HPht)2(g-Pic)2] (58.10(2) ) [33],
[Zn(Pht)(g-Pic)]n (57.11(1) ) [35]. The Pht2
anion in
this complex behaves as a tridentate ligand using one
carboxylate group to coordinate to the Co(II) atom in a
monodentate coordination fashion and the other
carboxylate group to ligate the adjacent metal in a 1,3-
chelating mode. The CO bond distances of the
Fig. 1. The fragment of a polymeric chain in compound 1.
carboxylate groups are in the range of 1.248(2)
1.268(1) A and the OCO angle for monodentate
(Co(1)O(1w) 2.113(1) A), that comprise the equatorial carboxylate group is 125.45(11) , slightly greater than
plane. The axial positions are lled by the remaining 120.71(11) for the chelating one. The dihedral angles
carboxylato-oxygen atom O(4a) of the Pht residue between the carboxylate plane described by atoms
(Co(1)O(4a) 2.261(1) A) and the oxygen atom O(1) of O(1)C(9)O(2) and O(3)C(16)O(4) and aromatic ring of
 ARTICLE IN PRESS
S.G. Baca et al. / Journal of Solid State Chemistry 177 (2004) 28412849 2845

the phthalate anion are 104.8(2) and 30.6(2) , respec- the whole crystal does not demonstrate chirality. Similar
tively. helical structures with the bridging phthalate ligand
The most interesting feature of compound 1 is the have been found in the zinc(II) mixed-ligand phthalate
formation of a helical structure. The Pht ligands bridge complexes [Zn(Pht)(tu)2]n [25] and [Zn(Pht)(bpy)(H2O)]n
cobalt atoms forming an innite 1D helical chain [31]. The intra-helix Co?Co separation is 6.247(1) A,
running along the [101] direction in the unit cell (Fig. longer than that in the helix of [Zn(Pht)(bpy)(H2O)]n
2). As shown in Fig. 3, one helical chain in compound 1 (5.633 A [31]) but shorter than the corresponding
exhibits right handedness (a) while the adjacent chain is metal?metal distance of 7.367(1) A found in the linear
left handed (c). Because left-handed and right-handed chain of [Co(Pht)(2-MeIm)2]n [34]. It is interesting to
helical chains coexist in the crystal structure (Fig. 3b), note that each phthalate ligand is further involved in
strong OH?O hydrogen bonding with the coordi-
nated water molecule (O(1w)H(1)?O(4)=2.722(1) A).
This hydrogen bond links the adjacent helixes, as
illustrated in Figs. 2 and 4, forming layers along the
[101] direction. The nearest inter-helix Co?Co distance
is 5.164(1) A. There are also two additional NH?O
interactions between the carboxylate oxygens (O(1) and
O(2)) of the phthalate and uncoordinated nitrogens
(N(2) and N(4)) from 4-MeIm molecules
(N(2)?O(1)=2.872(1) A and N(4)?O(2)=2.799(1) A)
and one OH?O contact involving coordinated H2O
(O(1w)?O(2)=2.697(1) A) within the helical chains.
Corresponding hydrogen bonding data are given in
Table 3.

3.2.2. [Cu(Pht)(4-MeIm)2(H2O)]n (2)

The structure of 2 is similar to 1 and consists of a
polymeric helical chain of repeating Cu4-MeIm2
H2 O
building units linked together via the phthalate
anions (Fig. 5). Each copper atom is coordinated by a
pair of 4-MeIm units, a pair of phthalate ligands and a
Fig. 2. Crystal packing of the 1D helical chains in 1. The hydrogen
water molecule; however, two o-phthalate ions are
atoms and cyclic fragments are omitted for clarity. Hydrogen bonds ligated to a Cu(II) atom through carboxylate oxygen
are shown as dotted lines. in a monodentate fashion. As a consequence, a square-
pyramidal N2O3 coordination geometry is observed
around the Cu(II) atom. The basal plane of the
{CuN2O3} square pyramid is dened by N(1) and N(3)
from the 4-MeIm molecules, and O(3a) and O(1w) of the
carboxylate group and water molecule. The apical
position is occupied by O(1) of the carboxylate group
belonging to another Pht residue. The equatorial CuN
(1.978(2), 1.981(2) A), CuOcarboxylate (2.009(2) A) and
CuOwater (2.040(2) A) distances are in agreement with
those observed in [Cu2(Pht)2(g-Pic)4(H2O)]n (CuN
1.985(7)2.012(7), CuO 1.995(7)2.053(5) A [33]). The
axial Cu(1)O(1) distance of 2.353(2) A is longer than
that in the related complex (2.240(4) A [33]). The bond
angles at Cu atom range from 87.94(8) to 101.47(7)
(Table 2).
The Pht2
anion behaves as a bidentate ligand
bridging two adjacent Cu(II) atoms through oxygen
atoms from both carboxylate groups (1,6-bridging
mode). The C(9)O(1) and C(16)O(3) bond distances
Fig. 3. A space-lling representation of the (a) right-handed chain,
and (c) left-handed chain. Hydrogen atoms and 4-methylimidazole of the carboxylate groups are similar or slightly longer
fragments are omitted for clarity. (b) A view of the crystallographic xy (1.253(3) and 1.268(3) A, respectively) than the C(9)
plane in 1. O(2) and C(16)O(4) distances of 1.254(3) and
 ARTICLE IN PRESS
2846 S.G. Baca et al. / Journal of Solid State Chemistry 177 (2004) 28412849

Fig. 4. A perspective view of the 1D helical chains in the crystal structure of 1 along y-axis. The hydrogen atoms and cyclic fragments are omitted for
clarity. Hydrogen bonds are shown as dotted lines.

Table 3
Hydrogen bonding interactions

DH?A d(DH) (A) d(H?A) (A) angle DHA (deg) d(D?A) (A)

1
N(2)H(2)?O(1)a 0.88 2.061 152 2.872(1)
N(4)H(4)?O(2)b 0.88 1.927 170 2.799(1)
O(1w)H(1a)?O(4)c 0.83(2) 1.90(2) 171(3) 2.722(1)
O(1w)H(1b)?O(2) 0.84(3) 1.92(3) 155(3) 2.697(1)

2
N(2)H(2)?O(1)a 0.88 2.013 153 2.826(3)
N(4)H(4)?O(2)b 0.88 1.901 171 2.772(3)
O(1w)H(1a)?O(4)c 0.78(6) 1.90(5) 170(6) 2.676(3)
O(1w)H(1b)?O(2) 0.84(4) 1.89(4) 155(4) 2.673(3)
a
1=2
x; y 1=2; 1=22z:
b
x; y
1; z:
c
1=2 x; 1=2
y; 1=2 z:

1.247(3) A, respectively, which do not take part in polymeric helical chains are knitted together by O
coordination to metal ions. The CC bond distances, H?O hydrogen bonds between the oxygen O(4) atom
being between 1.372(5) and 1.400(3) A, and the CCC of the carboxylate and the hydrogen atom of coordi-
angles of the aromatic ring of the Pht molecules, varying nated water molecules (O(1w)H?O(4)=2.676(3) A) to
from 118.9(3) to 121.0(3) , fall in the range of values create 2D layers parallel to the [101] direction in the unit
found in the pure ligand [48] and in 1 or other complexes cell. Between the adjacent helixes the shortest Cu?Cu
[33,34]. The dihedral angles formed between the distance is 5.251(1) A. Additional strong OH?O
carboxylate plane and the aromatic ring in the phthalate hydrogen bonds between a coordinated water molecule
anion are 106.5(2) for O(1)C(9)O(2) and 28.0(2) for and uncoordinated carboxylate oxygen atoms O(2)
O(3)C(16)O(4), quite similar to those found in 1. (O(1w)?O(2)=2.673(3) A) and NH?O bonds invol-
As in 1, the phthalate ligand links the [Cu(4- ving uncoordinated 4-methylimidazole nitrogen atoms
MeIm)2(H2O)] units into an innite helical chain along (N(2) and N(4)) and oxygen atoms (O(1) and O(2)) of
the [110] direction in the unit cell of 2. The intra-helix the phthalate of 2.826(3) and 2.772(3) A, respectively,
Cu?Cu distance is 6.254(1) A which is comparable to were found within the helixes. Corresponding hydrogen
the intra-helix Co?Co distance in 1 (6.247(1) A). The bonding data are given in Table 3.
 ARTICLE IN PRESS
S.G. Baca et al. / Journal of Solid State Chemistry 177 (2004) 28412849 2847

3.3. Magnetic properties

The thermal dependence of wM T (wM T being the

product of the molar magnetic susceptibility and the
temperature) and the simulated curves for powdered
samples of the polymeric helical chain compounds 1 and
2 are shown in Figs. 6 and 7. The molar magnetic
susceptibilities have been corrected for their diamagnetic
and temperature independent paramagnetic (TIP) con-

Fig. 7. Temperature dependence of wM T for compound 2. The circles

correspond to the experimental data, the simulation for the linear
chain model is depicted as a line.

tributions. For compound 1, the TIP is 4.6  10
4 emu/

mol. The room temperature wM T value of 3.16 emu K/
mol for compound 1 (Fig. 6) agrees well with the
calculated value of 3.17 emu K/mol for a high-spin
Co(II) compound (S 3=2; g 2:6) [49]. The gradual
decrease of wM T by lowering the temperature is typical
for high-spin Co(II). This decrease of wM T is due to
zero-eld splitting. A simulation within the temperature
Fig. 5. The fragment of polymeric chain in compound 2. range 20300 K with a g-value of 2.6 and an axial zero-
eld splitting parameter of jDj 62 cm
1 agrees best
with the experimental data. The wM T values of
compound 2, with a TIP of 0.6  10
4 emu/mol, remain
constant at 0.44 emu K/mol down to 50 K (Fig. 7). This
agrees well with the calculated wM T value of 0.41 emu K/
mol for a single Cu(II) ion (S 1=2; g 2:1) [50].
Below 50 K, wM T decreases due to a weak intramole-
cular antiferromagnetic interaction of neighboring
Cu(II) ions in the chain. Below 25 K, probably weak
intermolecular ferromagnetic interactions between
Cu(II) ions of neighboring chains provoke an increase
of wM T: With the BonnerFisher model [51], for which
the interaction is approximated as one between the
Cu(II) ions in a linear, equally spaced chain, the
experimental data, between 25 and 300 K, could be
simulated best with g 2:18 and J
0:4 cm
1.

Acknowledgments

Fig. 6. Temperature dependence of wM T for compound 1. The circles The authors gratefully acknowledge support from the
correspond to the experimental data, the simulation is depicted as a Swiss National Science Foundation (SCOPES
line. 7MDPJ065712.01/1).
 ARTICLE IN PRESS
2848 S.G. Baca et al. / Journal of Solid State Chemistry 177 (2004) 28412849

References (c) H. Li, M. Eddaoudi, M. OKeeffe, O.M. Yaghi, Nature 402

(1999) 276;
[1] (a) S.R. Batten, R. Robson, Angew. Chem. Int. Ed. 37 (1998) (d) J. Tao, M.-L. Tong, J.-X. Shi, X.-M. Chen, S.W. Ng, Chem.
1460; Commun. (2000) 2043;
(b) P.J. Hagrman, D. Hargman, J. Zubieta, Angew. Chem. Int. (e) M. Eddaoudi, J. Kim, J.B. Wachter, H.K. Chae, M. OKeeffe,
Ed. 38 (1999) 2638; O.M. Yaghi, J. Am. Chem. Soc. 123 (2001) 4368;
(c) A.J. Blake, N.R. Champness, P. Hubberstey, W.-S. Li, M.A. (f) S.A. Bourne, J. Lu, A. Mondal, B. Moulton, M.J. Zaworotko,
Withersby, M. Schroder, Coord. Chem. Rev. 183 (1999) 117; Angew. Chem. Int. Ed. 40 (2001) 2111;
(d) R. Robson, J. Chem. Soc. Dalton Trans. (2000) 3735; (g) B. Moulton, J. Lu, A. Mondal, M.J. Zaworotko, Chem.
(e) M. Eddaoudi, D.B. Moler, H. Li, B. Chen, T.M. Reineke, M. Commun. (2001) 863;
OKeeffe, O.M. Yaghi, Accounts Chem. Res. 34 (2001) 319; (h) C.-G. Zheng, Z.-F. Chen, J. Zhang, R.-G. Xiong, X.-Z. You,
(f) B. Moulton, M.J. Zaworotko, Chem. Rev. 101 (2001) 1629; Inorg. Chem. Commun. 4 (2001) 165;
(g) B. Moulton, M.J. Zaworotko, Curr. Opin. Solid State Mater. (i) J. Tao, X. Yin, R. Huang, L. Zheng, Inorg. Chem. Commun. 5
Sci. 6 (2002) 117. (2002) 1000;
[2] (a) E.G. Bakalbassis, A.P. Bozopoulos, J. Mrozinski, P.J. (j) N. Shan, A.D. Bond, W. Jones, Crystal Eng. 5 (2002) 9;
Rentzeperis, C.A. Tsipis, Inorg. Chem. 27 (1988) 529; (k) S.Y. Yang, L.S. Long, R.B. Huang, L.S. Zheng, Chem.
(b) P. Sobota, J. Utko, T. Lis, J. Organomet. Chem. 393 (1990) Commun. 5 (2002) 472;
349; (l) Y.-F. Zhou, Y.-J. Zhao, D.-F. Sun, J.-B. Weng, R. Cao, M.-C.
(c) E.G. Bakalbassis, C.A. Tsipis, A.P. Bozopoulos, W. Dreissig, Hong, Polyhedron 22 (2003) 1231.
H. Hartl, J. Mrozinski, Inorg. Chim. Acta 186 (1991) 113; [4] M.B. Cingi, C. Guastini, A. Musati, N. Nardelli, Acta Crystal-
(d) S. Cueto, V. Gramlich, W. Petter, P. Rys, Acta Crystallogr. C logr. B 26 (1970) 1836.
47 (1991) 75; [5] C.K. Prout, J.R. Carruthers, F.J.C. Rossotti, J. Chem. Soc. (1971)
(e) Z.-L. Deng, J. Shi, Z.-H. Jiang, D.-Z. Liao, S.-P. Yan, G.-L. 3350.
Wang, H.-G. Wang, R.-J. Wang, Polyhedron 11 (1992) 885; [6] M.B. Cingi, A.M.M. Lanfredi, A. Tiripicchio, M.T. Camellini,
(f) M. Dusek, V. Petricek, J. Kamenicek, Z. Sindelar, Acta Acta Crystallogr. B 33 (1977) 659.
Crystallogr. C 48 (1992) 1579; [7] (a) M.B. Cingi, A.M.M. Lanfredi, A. Tiripicchio, M.T. Camelli-
(g) E.G. Bakalbassis, P. Bergeret, O. Kahn, S. Jeanin, Y. Jeanin, ni, Acta Crystallogr. B 34 (1978) 134;
Y. Dromzee, M. Guillot, Inorg. Chem. 31 (1992) 75; (b) M.B. Cingi, A.M.M. Lanfredi, A. Tiripicchio, M.T. Camelli-
E.G. Bakalbassis, P. Bergeret, O. Kahn, S. Jeanin, Y. Jeanin, ni, Acta Crystallogr. B 34 (1978) 406.
Y. Dromzee, M. Guillot, Inorg. Chem. 31 (1992) 625; [8] M.B. Cingi, A.M.M. Lanfredi, A. Tiripicchio, M.T. Camellini,
(h) J. Cano, G. De Munno, J. Sanz, R. Ruiz, F. Lloret, J. Faus, Acta Crystallogr. B 34 (1978) 412.
M. Julve, J. Chem. Soc. Dalton Trans. (1994) 3465; [9] J.W. Bats, A. Kallel, H. Fuess, Acta Crystallogr. B 34 (1978)
(i) J. Cano, G. De Munno, J.L. Sanz, R. Ruiz, J. Faus, F. Lloret, 1705.
M. Julve, A. Caneschi, J. Chem. Soc. Dalton Trans. (1997) 1915; [10] M.B. Cingi, A.M.M. Lanfredi, A. Tiripicchio, M.T. Camellini,
(j) A.D. Burrows, D.M. Mingos, S.E. Lawrence, A.J.P. White, D. Acta Crystallogr. B 35 (1979) 312.
Williams, J. Chem. Soc. Dalton Trans. (1997) 1295; [11] M.B. Cingi, A.M.M. Lanfredi, A. Tiripicchio, M.T. Camellini,
(k) C.S. Hong, Y. Do, Inorg. Chem. 36 (1997) 5684; Acta Crystallogr. B 37 (1981) 2159.
(l) H. Li, M. Eddaoudi, T.L. Groy, O.M. Yaghi, J. Am. Chem. [12] I. Krstanovic, Lj. Karanovic, Dj. Stojakovic, Acta Crystallogr. C
Soc. 120 (1998) 8571; 41 (1985) 43.
(m) R.H. Groeneman, L.R. MacGillivray, J.L. Atwood, Inorg. [13] K. Shakhatreh, E.G. Bakalbassis, I. Brudgam, H. Hartl, J.
Chem. 38 (1999) 208; Mrozinski, C.A. Tsipis, Inorg. Chem. 30 (1991) 2801.
(n) L. Deakin, A.M. Arif, J.S. Miller, Inorg. Chem. 38 (1999) [14] D. Poleti, Lj. Karanovic, B.V. Prelesnik, Acta Crystallogr. C 49
5072; (1993) 1249.
(o) H.-K. Fun, S.S.S. Raj, R.-G. Xiong, J.-L. Zuo, Z. Yu, X.-Z. [15] E.G. Bakalbassis, A. Terzis, Inorg. Chim. Acta 218 (1994) 167.
You, J. Chem. Soc. Dalton Trans. (1999) 1915; [16] D.J. Williams, S.J. Maginn, R.J. Davey, Polyhedron 13 (1994)
(p) M. Eddaoudi, H. Li, O.M. Yaghi, J. Am. Chem. Soc. 122 1683.
(2000) 1391; [17] G. Smith, A.N. Reddy, K.A. Byriel, C.H.L. Kennard, J. Chem.
(q) S.M.-F. Lo, S.S.-Y. Chui, L.-Y. Shek, Z. Lin, X.-X. Zhang, Soc. Dalton Trans. (1995) 3565.
G. Wen, I.D. Williams, J. Am. Chem. Soc. 122 (2000) 6293; [18] J.L.L. Vaz, G. Duc, M. Petit-Ramel, R. Faure, O. Vittori, Can. J.
(r) B. Gomez-Lor, E. Gutierrez-Puebla, M. Iglesias, M.A. Chem. 74 (1996) 359.
Monge, C. Ruiz-Valero, N. Snejko, Inorg. Chem. 41 (2002) [19] D.R. Whitcomb, R.D. Rogers, Inorg. Chim. Acta 256 (1997) 263.
2429; [20] A. Escuer, R. Vicente, F.A. Mautner, M.A.S. Goher, Inorg.
(s) K. Barthelet, J. Marrot, D. Riou, G. Ferey, Angew. Chem. Chem. 36 (1997) 1233.
Int. Ed. 41 (2002) 281; [21] E.G. Bakalbassis, D.G. Paschalidis, C.P. Raptopoulou, V.
(t) A. Escuer, F.A. Mautner, N. Sanz, R. Vicente, Inorg. Chim. Tangoulis, Inorg. Chem. 37 (1998) 4735.
Acta 340 (2002) 163; [22] Z.-N. Chen, H.-X. Zhang, K.-B. Yu, B.-S. Kang, H. Cai, C.-Y.
(u) H.-D. Bian, J.-Y. Xu, W. Gu, S.-P. Yan, D.-Z. Liao, Z.-H. Su, T.-W. Wang, Z.-L. Lu, Inorg. Chem. 37 (1998) 4775.
Jiang, P. Cheng, Inorg. Chem. Commun. 6 (2003) 573; [23] M.R. Bermejo, M. Fondo, A. Garca-Deibe, A.M. Gonzalez,
(v) L. Li, Z. Liu, S.S. Turner, D. Liao, Z. Jiang, S. Yan, Eur. J. A. Sousa, J. Sanmartn, C.A. McAuliffe, R.G. Pritchard, M.
Inorg. Chem. 1 (2003) 62; Watkinson, V. Lukov, Inorg. Chim. Acta 293 (1999) 210.
(w) L. Li, D. Liao, Z. Jiang, S. Yan, Inorg. Chim. Acta 357 [24] P. Lightfoot, A. Snedden, J. Chem. Soc. Dalton Trans. (1999)
(2004) 405. 3549.
[3] (a) S.T. Xiang, F.X. Dao, X.T. Wen, B.Y. Kai, Polyhedron 16 [25] A.D. Burrows, R.W. Harrington, M.F. Mahon, C.E. Price,
(1997) 1411; J. Chem. Soc. Dalton Trans. (2000) 3845.
(b) X.S. Tan, J. Sun, D.F. Xiang, W.X. Tang, Inorg. Chim. Acta [26] M. Devereux, M. McCann, V. Leon, M. Geraghty, V. McKee,
255 (1997) 157; J. Wikaira, Met.-Based Drugs 7 (2000) 275.
 ARTICLE IN PRESS
S.G. Baca et al. / Journal of Solid State Chemistry 177 (2004) 28412849 2849

[27] Y. Zhang, J. Li, Q. Su, Q. Wang, X. Wu, J. Mol. Struct. 516 [39] G.M. Sheldrick, SHELXL-97, University of Gottingen, Gottin-
(2000) 231. gen, Germany, 1999.
[28] E. Suresh, K. Boopalan, R.V. Jasra, M.M. Bhadbhade, Inorg. [40] J.J. Borras-Almenar, J.M. Clemente - Juan, E. Coronado, B.S.
Chem. 40 (2001) 4078. Tsukerblatt, Inorg. Chem. 38 (1999) 6081.
[29] H.-X. Zhang, B.-S. Kang, A.-W. Xu, Z.-N. Chen, Z.-Y. Zhou, [41] G.B. Deacon, R.J. Phillips, Coord. Chem. Rev. 33 (1980) 227.
A.S.C. Chan, K.-B. Yu, C. Ren, J. Chem. Soc. Dalton Trans. [42] K. Nakamoto, Infrared and Raman Spectra of Inorganic and
(2001) 2559. Coordination Compounds, Wiley, New York, 1986, p. 230.
[30] Y. Wan, L. Jin, K. Wang, L. Zhang, X. Zheng, S. Lu, New [43] R.C. Mehrotra, R. Bohra, Metal Carboxylates, Academic Press,
J. Chem. (2002) 1590. New York, 1983, p. 47.
[31] Jing-Cai Yao, W. Huang, B. Li, S. Gou, Y. Xu, Inorg. Chem. [44] (a) J. Kitchen, J.L. Bear, Thermochim. Acta 1 (1970) 537;
Commun. 5 (2002) 711. (b) J. Sun, L. Yuan, K. Zhang, D. Wang, Thermochim. Acta 343
[32] S.G. Baca, I.G. Filippova, O.A. Gherco, M. Gdaniec, Yu.A. (2000) 105.
Simonov, N.V. Gerbeleu, P. Franz, R. Basler, S. Decurtins, Inorg. [45] E.M. Abd Alla, M.I. Abdel-Hamid, J. Therm. Anal. Cal. 62
Chim. Acta, in press. (2000) 769.
[33] N.V. Gerbeleu, Yu.A. Simonov, G.A. Timko, P.N. Bourosh, [46] (a) W.D. Horrocks Jr., J.N. Ishley, R.R. Whittle, Inorg. Chem.
J. Lipkowski, S.G. Baka, D.I. Saburov, M.D. Mazus, Russ. 21 (1982) 3265;
J. Inorg. Chem. 44 (1999) 1191. (b) W.D. Horrocks Jr., J.N. Ishley, R.R. Whittle, Inorg. Chem.
[34] Yu.A. Simonov, M. Gdaniec, I.G. Filippova, S.G. Baca, G.A. 21 (1982) 3270.
Timco, N.V. Gerbeleu, Russ. J. Coord. Chem. 27 (2001) 353. [47] X.-M. Chen, B.-H. Ye, X.-Ch. Huang, Z.-T. Xu, J. Chem. Soc.
[35] S.G. Baca, Yu.A. Simonov, N.V. Gerbeleu, M. Gdaniec, P.N. Dalton Trans. (1996) 3465.
Bourosh, G.A. Timco, Polyhedron 20 (2001) 831. [48] O. Elmer, Helv. Chim. Acta 6 (1981) 1902.
[36] S.G. Baca, I.G. Filippova, N.V. Gerbeleu, Yu.A. Simonov, M. [49] S.M. Ostrovsky, R. Werner, D.A. Brown, W. Haase, Chem. Phys.
Gdaniec, G.A. Timco, O.A. Gherco, Yu.L. Malaestean, Inorg. Let. 353 (2002) 290.
Chim. Acta 344 (2003) 109. [50] C.G. Pierpont, L.C. Francesconi, D.N. Hendrickson, Inorg.
[37] Stoe & Cie, X-Area V1.17 & X-RED32 V1.04 Software, Stoe & Chem. 16 (1977) 2367.
Cie GmbH, Darmstadt, Germany, 2002. [51] O. Kahn, Molecular Magnetism, Wiley-VCH, New York, 1993,
[38] G.M. Sheldrick, Acta Crystallogr. A 46 (1990) 467. p. 252.