JOURNAL.

OF SOLID STATE CHEMISTRY 52, 274-280 (1984)

Crystal Structures and Phase Transition of RbpTeBr6 (300-12.5 K)

W. ABRIEL”
Sonderforschungsbereich 127 und Fachbereich Chemie der Universitiit,
Lahnberge, D-3550 Marburg, Federal Republic of Germany

AND J. IHRINGER
Institut fiir Kristallographie der Universitiit, Charlottenstr. 33, D-7400
Tiibingen, Federaf Republic of Germany

Received July 19, 1983; in revised form October 24, 1983

Using 298 and 160(3)K diffractometer intensity data the structure of Rb*TeBr, has been determined by
single crystal X-ray technique and refined to a final R,. of 0.041 and 0.037, respectively (K2PtC16type
structure, space group Fm3m, 2 = 4 with a298= 10.773(4) A and a,60 = 10.713(6) A). The powder
diffraction pattern from 300 to 12.5 K was recorded by a low-temperature Guinier diffractometer and
camera. Below 45(5) K a second-urder phase transition leads to a tetragonally distorted structure
corresponding to a softening of the T&) rotary phonon. The powder pattern measured with the
diffractometer-at 12.5 K was used for structural refinement (R = 0.092). This low-temperature phase
shows a ferrorotative displacement of the TeBrsoctahedra with a tilt angle of 4.7(l) deg. (space group
14/m, Z = 2, a = 7.4726(3) d; and c = 10.7008(S)A). The structural results indicate that there is no
stereochemical activity of the lone pair electrons at Te(IV) even at very low temperatures. Phase
transitions of Rb2TeBr6 and RbzTeId (A,,(X)-condensation) are compared. The results of a lattice
dynamic calculation shows that only the T,,(T) condensation can be explained with a rigid ion model.

Introduction were carried out at room temperature, a

stereochemical effect of the lone pair elec-
In 1957 Gillespie and Nyholm (I) pre- trons at lower temperatures could be possi-
dieted that hexa-coordinated complexes of ble.
Te(IV) should not possess a regular octahe- For compounds AzTeBr6 (with A = K,
dral structure but rather one based on seven NH4, Rb, Cs) the high-temperature phases
coordination with a lone pair of electrons show the cubic K,PtCl,type structure (Fig.
occupying the seventh position. However, 1). Lowering the temperature, second-or-
all structures so far reported, picking corn- der phase transitions can be observed, es-
pounds A2TeBr6 with A = K, NH4, Rb, Cs, pecially when the anions are comparatively
(CH&N (2-5), for example, indicate that large. These phase transitions can be ex-
such complexes are in fact regular octahe- plained by a softening of rotary phonons.
dra. As all these structural investigations Generally, in A&fX6 compounds this insta-
bility is result of a double minimum in the
* To whom correspondence should be addressed. Coulomb potential with respect to the octa-
Present address: Institut fiir Anorganische Chemie der hedra tilt angle p around (0 0 1); the depth
UniversitBt, Callinstrasse 9, D-3000 Hannover, FRG. of this minimum depends on the interaction
0022-4596184$3.00 274
Copyright 0 1984 by Academic Press. Inc.
All rights of reproduction in any form rew ;ved.
 PHASE TRANSITIONS OF Rb2TeBr6 275

study (II) will give us a hint for under-

standing the lattice dynamics of A&IX6
phases.

Experimental
Crystals of RbzTeBrGprecipitated from a
equimolar solution of TeOz and Rb2C03 in
cont. hydrobromic acid. Weissenberg and
precession photographs from a cubeoctahe-
dral single crystal (V = 0.003 mm3), embed-
ded in adhesive in order to protect it from
FIG. 1. K#tC16 structure (from (6)); small spheres moisture, showed F-centered Laue symme-
K; octahedra PtQ,. try r&n according to the crystal symmetry
of the K,PtCl,-type structure. A Guinier
and the radii of the corresponding ions (7). photograph of the powder (Huber Guinier
Table I shows the known phase transi- System 600, Ge-standard with a = 5.65775
tions for some compounds AzTeBr6. Low- A) at 298 K agreed with the lattice parame-
ering the temperature, the first transition ters found from the single crystal. A least-
leads to a tetragonally distorted structure, squares refinement of the lattice dimension
space group PGnnc, indicating a condensa- yielded the final value using the powder
tion of the AZ&X) librational mode (A = K, data recorded by film methods. Single crys-
NH+ As a result of antiferrorotative tilted tal intensity measurements of the Fm3m
TeXs-octahedra, this structure is stable for structure at 298 and 160(3) K were per-
RbzTeIGat room temperature (II). formed on a CAD4 diffractometer (Enraf
Related compounds like Elpasolites Nonius) using graphite-monochromatized
(RbzNaHoFs, for example, Ref. (12)) show MO& radiation in an R scan mode (scan
a phase transition corresponding to a soft- angle 2.5”, scan time max. 90 set with omax.
ening of the Ti,(T) rotary phonon (ferroro- = 30”). The lattice dimension at 160 K was
tative-tilted HoF6-octahedra). From the lat- calculated from 21 reflexions in the range
tice dynamical point of view, the 10” < 8 < 24” centered by the diffractome-
knowledge of the cause for these different ter. Severe absorption effects (p = 286
kinds of symmetry reduction should be de- cm-‘) required the application of numerical
sirable. A discussion of the results of this absorption corrections limited by the accu-
low-temperature investigation of RbzTeBr6 racy of crystal size measurement. For the
in comparison with the data from a RbzTeIe structural calculations the program system

TABLE I
SPACE GROUPS FOR COMPOUNDS A2TeBr6 AT DIFFERENT TEMPERATURES

A= Ref.
K ? P2tln 1 ? Pnnm 1 Pbhnnc 1 FmJm 181
NH& ? 3 PUnnc~ Fm3m I3.91
cs 1 Fm3m _ IZlOl

160 200 I 300 4001 I 400

221 410 446 TempIKI
276 ABRIEL AND IHRINGER

TABLE II
SOME DETAILS FROM THE SINGLE CRYSTAL INVESTIGATIONS. R,,, SHOWS THE CONSISTENCY IN THE
F-VALUES OF EQUIVALENT REFLEXIONS. R w = CAFV%XF,,m; RG = [B W(AF)2]“2/[Z W(F,,)*]“*

Temp. Measured Unique refl.

WI reflexions F ’ @II Rim R RW RG Weight

298 636 118 0.052 0.06 0.041 0.037 1.588/a*(F)

160(3) 530 117 0.056 0.05 0.037 0.032 1.161/cr2(F)

SHELX76 (13) was applied using the scat- ment with formfactors corrected for f’ and
tering factors for Rb+, Te, and Br (from the f” (see above) all possible atomic coordi-
International Tables (14)) considering the nates and the isotropic thermal parameters
anomalous dispersion corrections accord- were varied besides the 6 profile and cell
ing to Cromer and Libermann (15). Some parameters. So the total number of free pa-
details from the structure analysis can be rameters was 15 for 14/m, e.g. The single
taken from Table II. reflexion recordings were prepared by fit-
A powder with particle size less than 50 ting one or more Gaussian or Lorentzian
pm prepared by crushing single crystals profiles to the measured line shapes. The
was sieved on a silicone-moistened 0.02- lattice constants at 12.5 K were evaluated
mm-thick Mylar foil. The measurements in by the Rietveld program.
a temperature range from 300 to 12.5 K
were performed with the low-temperature
Results
Guinier diffractometer and camera (16)
with Ge-monochromator and CuKcrl radia- The parameters found from the single
tion from a rotating anode generator. For a crystal data at 298 and 160(3) K are listed in
qualitative survey the diffraction pattern Table III. A correction of the positional pa-
(Fig. 2) was recorded at continuously vary- rameter of the Br-atom was applied for the
ing temperatures with the film lift device. apparent shortening of the Te-Br bond due
For the Rietveld refinement (17) 1952inten- to thermal motion (28) on the assumption
sities (6.96“ 5 8 5 46.00”, step size 0.02%, that the rigid TeB$-ion is librating about
measuring time 20 set at each step) were the central tellurium atom. The new param-
collected with the diffractometer at 12.5 K. eters were calculated to x = 0.2510(3) at 298
The background substraction in the prepa- K and x = 0.2519(2) at 160(3) K. The cor-
ration program based on a linear interpola- rectness of the rigid ion model can be
tion between 33 background values selected checked by calculating a generalized R-in-
from a plot of the diagram. In the refine- dex for the agreement of observed and cal-

FIG. 2. Guinier diffraction pattern, 300-12.5 K.

 PHASE TRANSITIONS OF Rb2TeBr, 277

TABLE III phase transition is of second-order. No fur-

FINAL~ARAMETERSFOR Rb2TeBr, AT 298 AND ther change of symmetry is found between
160(3)K (x 104).SPACE GROUP Fm3m,Z = 4 WITH T, and 12.5 K.
a = 10.773(4) A AT 298 K AND a = 10.713(6)A AT The possible low-temperature space
160(3) K. Te IN 4a (O,O,O);Rb IN 8c (f,),f);
group is therefore the result of a soft mode
Br IN 24e (x,0,0)
I-point condensation (see also a recent pa-
Temp. per of Ihringer (12)). Figure 3 displays all
WI ‘k UII Rb UII Br.X Br Ult Br Gz possible space groups resulting from a sec-
298 180(7) 499(11) 2496(2) 190(11) 6OOuO)
ond-order phase transition with k, = 0. Each
W3) 87(6) 281(9) 2510(2) 109( 10) 356(7) normal mode displacement transforms un-
der the symmetry of m3m according to the
irreducible representation in the head of the
culated Uij (program XANADU (19), RG = table. However, in each representation-
0.007, and 0.028 at 298 and 160 K, respec- except A,,-there are symmetries that
tively). The final maximum peak height transform the displacements not in itself,
from a F0 -- F, Fourier map was J electrons just those symmetries are lost below T,. So
Am3in the position (O,O,O)at both tempera- the remaining elements define the space
tures. group after the softening of the normal
The splitting of the cubic reflexions at T, mode. Therefore for the profile refinement
= 45(5) K (see Fig. 2) leads to a continu- the competing space groups Z4/mmm,
ously increasing tetragonal lattice distor- Z4mm, Z?2m, and 14/m were taken into ac-
tion. The change of the lattice constants count. The line profile refinement of the
and intensities at T, is continuous, so the 12.5 K diffraction pattern yielded the best

ML& Alp
Atom

Te

Rb

Br

1. 2. Rotation of the displacement fields around [ill)

Basisvector generates the two supplanent basisvectors

Fm3m

Space groups resulting from a condensation of one normal mode

FIG. 3. Normal mode displacement fields in Rb2TeBr,.

278 ABRIEL AND IHRINGER

TABLE IV Discussion
FINAL PARAMETERS FOR RbzTeBr6 AT 12.5 K. SPACE
An octahedral coordination for the
GROUP 14/m, Z = 2 WITH a = 7.4726(3) A AND c =
10.7008(5)A TeB$-ion even at 12.5 K is the most im-
portant result from the chemical point of
view. The small differences of the Te-Br
Atom Position x Y Z $1
bond lengths in the low temperature struc-
Te 2a 0 0 0.5(l) ture are not significant considering the stan-
Rb 4d 0 P dard deviations and are typical for a tetrag-
Br(1) 4e 0.2&6) ::;I:;
Br(2) 8h 0.2&) 0.2&7) 0 1.2(l) onal refinement of positional parameters.
So the point symmetry of the TeB$-ion is
still m3m. There appears to be no stereo-
chemical active lone pair of electrons at
residuals’ R = 0.092, RP = 0.19, and RPW= Te(IV) in this hexahalo complex ion.
0.20 for the model 14/m (structural parame- Finally, the phase transition is result of a
ters see Table IV).2 The best of the final ferrorotative displacement of the TeB$
residuals for the competing space groups octahedra (tilt angle 4.7( 1)“) corresponding
was R = 0.106, but while the coordinates in to a softening of the T,,(T) rotary phonon.
the refinement of the Z4/m-structure The symmetry of the condensing mode de-
reached their final values after 4 cycles, in pends on the group-subgroup relations of
the other models they oscillated around the space groups when Landau’s law is re-
their starting values in the limits of 3 cr. We alized (20).
so conclude that the minimum found for Z4/ Retaining the cubic structure and the
m describes the reality. bond distances within the TeBr,-octahe-
The interatomic distances are listed in dron, the other interatomic distances de-
Table V using the corrected positional pa- crease when cooling from 298 to 160 K. The
rameters for Br at 298 and 160 K. atomic and molecular motions are diminish-
ing. So a closer contact of the Br atoms
between the anions is possible. Below T,
‘R = Z, [Ff(obs) - (I/c)Fj(calc)]/C, Fy(obs);
RP = Z b,(oW - yi(calc)]‘/X, [y,(obs)]‘; TABLE V
R pw = C, w+[yi(obs) - y,(calc)]‘lZ, w,[y,(obs)]‘. INTERATOMIC DISTANCES (A)
The reason for the relative high profile residuals lies in
the insufficient corrections for the asymetric line Br-Br
shapes at low angles.
Temp. Within Between
* Tables of observed and calculated structure factors Rt+Br Rb-Te
[Kl Te-Br anion anion
and the F-(obs)/FZ(calc)- listing from the Rietveld re-
finement of the powder data as well as the raw profile
I. For RbJeBrs at different temperatures
data are deposited with the National Auxiliary Publi- 298 2.704(3) 3.824(3) 3.794(3) 3.809(2) 4&S(2)
cations Service. See NAPS document No. 04167for 13 160 2.699(2) 3.816(2) 3.759(2) 3.788(2) 4.639(2)
pages of supplementary material. Order from ASIW 12.5 2.696(6) 3.81X7) 3.701(7) 3.754(3) 4.595(l)
NAPS, Microfiche Publications, P.O. Box 3513 Grand 2. For the 12.5 K structure in detail
Central Station, New York, NY 10163. Remit in ad- Te -Br(l) 2x 2.68X7)
vance $4.00 for microfiche copy or for photocopy, -Br(2) 4x 2.702(5)

$7.75 up to 20 pages plus $.30 for each additional page. BrWBr(2) 2x 3.809(6)
Br(2)-Br(2) 2x 3.821(7) 1 Withi” ‘&J”
All orders must be prepaid. Institutions and Organiza-
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Foreign orders add $4.50 for postage and handling, for -Br(Z) 4x 3.917(4)
the first 20 pages, and $1.OOfor additional 10 pages of
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 PHASE TRANSITIONS OF Rb2TeBr6 279

FIG. 4. The cubic KrPtC&-type structure (left) and its tetragonally distorted substructures in a
projection along the fourfold axis: 14/m ferrorotative /3-RbrTeBr,-type (middle) and P4lmnc antifer-
rorotative /3-Rb;TeI,-type (right). The dotted lines show the a/b plane of the tetragonal unit cells.
Different heights of the octahedra are given by different strokes.

this distances decrease again as a result of the simple compounds AzTeBr6 with an
the more efficient packing. At 12.5 K the antifluorite arrangement of cations and an-
Br-Br distance between anions is more ions. As reported in the introductional sec-
than 0.1 A smaller than this distance within tion of this paper a X point condensation
the anion. The rigid Te-Br bond (mean seems to be the usual case, realized by an
2.700(4) A from this three determinations) exchange of the alkali or halogen position in
prevents a closer packing of the Br-atoms. RbzTeBr6 choosing a lighter or heavier
The coordination of Rb by Br changes from atom (K2TeBr6, RbzTe16,for example). Fig-
a 1Zfold (Fm3m) to a 4 + 4 + 4 (14/m) one, ure 4 shows the cubic K,PtCl, type struc-
while the (.mean) distances Rb-Br are de- ture and its tetragonal substructures in a
creasing from 298 to 12.5 K. projection along the fourfold axis. The
This I-point condensation of a rotary group-subgroup relationship of the space-
phonon found for the phase transition of groups (21) indicates the symmetry reduc-
Rb,TeBr6 seems to be an exception among tion:

4-2
F-3- -13~ I---422 r2. I- 4 k2

mm mmm m
K2PtC16 P-Rb,TeBr, @Rb2Te16

a-Rb2TeBr6

The order parameter for this second-or- mode (22). To understand the behavior in
der phase transition is the squared fre- this compound and to compare it with the
quency of the softening T#) rotation phase transitions in related materials (e.g.,
280 ABRIEL AND IHRINGER

RbZTe16, K2SnC16) we calculated the 2. I. D. BROWN, Canad. J. Chem. 42,2758 (1964).

phonon dispersion curves with the rigid ion 3. A. K. DAS AND I. D. BROWN, Canad. J. Chem.
model for the high-temperature Fm3m 44, 939 (1966).
4. R. W. BERGAND K. NIELSEN, Acta Chem. Stand.
phase. A 33, 157 (1979).
Starting with the atomic force constants 5. W. ABRIEL, Z. Kristallogr. 159, 1 (1982).
given by O’Leary and Wheeler for K2ReC16 6. D’ANs LAX, “Taschenbuch fiir Chemiker und
(23) the changes in the phonon frequencies Physiker,” Vol. III, Springer-Vet-lag, Berlin
were investigated by varying the force- and (1970).
7. J. IHRINGER, Acta Crystallogr. Sect. A 36, 89
charge parameters. Similar calculations for (1980).
K20sC16are reported by Sutton et al. (24). 8. W. ABRIEL, Mater. Res. Bull. 18, 1419 (1983).
It was one surprising result that the rota- 9. A. K. DAS AND I. D. BROWN, Canad. J. Chem.
tional mode energies at the zone center (IJ 47, 4288 (1969).
are always lower than these at the zone IO. W. ABRIEL. Habilitationsschrift, Universittit Mar-
burg (1983).
edge (X). The phase transition observed in Il. W. ABRIEL, Mater. Res. Bull. 17, 1341 (1982).
RbzTeBr6 (Fm3m - 14/m) thus agrees with 12. J. IHRINGER,Solid State Commun. 41, 525 (1982).
the rigid ion prediction, in contrast to the 13. G. M. SHELDRICK,in “Computing in Crystallogra-
antiferrorotative distortion of the octahedra phy,” p. 34, Delft Univ. Press (1978).
in RbzTe16(Fm3m - PWmnc). 14. “International Tables for X-Ray Crystallogra-
phy,” Vol. IV, Kynoch Press, Birmingham (1974).
Evidently the limits of the model are ex- 1.5. D. T. CROMERAND D. LIBERMANN, J. Chem.
ceeded with increasing radii of the anions Phys. 53, 1891 (1970).
or decreasing radii of the cations, respec- 16. J. IHRINGER,J. Appl. Crystallogr. 15, 1 (1982).
tively. The point charge model in the rigid 17. R. A. YOUNG, P. E. MACKIE, AND R. B. VON
ion calculation is a too rough approxima- DREELE,J. Appl. Crystallogr. 10, 262 (1977).
18. V. SCHOMAKERAND K. N. TRUEBLOOD,Acta
tion for the bigger ions, because there is no CrystalLogr. Sect. B 24, 63 (1968).
account of the polarization between shell 19. P. ROBERTSAND G. M. SHELDRICK,unpublished.
and nucleus. Nevertheless the structure I4/ 20. M. SUTTONAND R. L. ARMSTRONG,Phys. Rev. B
m indeed seems to be the more stable one, 25, 1813 (1982).
because we know no example of an AzMXh 21. TH. HAHN, Ed.. “International Tables for Crys-
tallography, Vol. A,” Reidel. Dordrecht and Bos-
compound in which the PUmnc-structure ton (1983).
remains stable when the temperature is fur- 22. E. J. VEENENDAHL, H. B. BROM, AND J.
ther lowered. IHRINGER,Physica B 114, 31 (1982).
23. G. P. O’LEARY AND R. G. WHEELER,Phys. Rev.
References B 1, 4409 (1970).
24. M. SUTTON, R. L. ARMSTRONG,B. M. POWELL,
1. R. J. GILLESPIEAND R. S. NYHOLM, Quart. Rev. AND W. J. L. BUYERS, Phys. Rev. B 27, 380
(London) 11, 339 (1957). (1983).