A REFINEMENT OF THE CRYSTAL STRUCTURES OF (NH4),TeBr6

AND Cs2TeBr6
A. K. DAS AND I. D. BROWN
Deparhnent of Physics, Hanailton College, iMcMaster University, Hanailtort, Ontario
Received December 1, 1965
ABSTRACT
(NH4)zTeBrs and CszTeBrs crystals have the cubic KzPtClc structure with space group:
FmSm(0R) with ao = 10.728 f 0.003 A and 10.918 f 0.002 A respectively. The positional
coordinate of the bromine atom, and the anisotropic temperature factors of all atoms in the
unit cell, have been refined for both crystals by a full matrix least-squares analysis of the
three dimensional X-ray diffraction data (R = 0.08). The Te-- Br distance, corrected for
probable thermal motions of atoms forming the bond, is 2.70 + 0.01 A in both crystals.
INTRODUCTION
In a previous paper, one of us (I. D. B.) reported the crystal structure of KzTeBr6 (I),
which possesses a distorted KoPtC16 structure (2). To examine the influence of the cation
on the bonding within the TeBrG2- ion, we have now refined the structures of (NH4)zTeBr6
and CszTeBr6, both of which possess the undistorted KsPtCl6 structure a t room tem-
perature.
Accurate lattice parameters for both crystals have already been determined by Swanson
and his co-workers (3, 4). The unit cell and space group of (NH4)zTeBr6 have been
determined by A'IanojloviC (5) and the structure of CszTeBr6 crystal has been reported
by Bagnall et al. (6). In the present ~vork, new X-ray diffraction dat a have been obtained
and more accurate values of Te-Br bond distances are reported.
EXPERI MENTAL
Bright-red crystals of (NH4)zTeBrc and Cs2TeBr6 were prepared by methods similar to those described
for KzTeBrs and (NH4)2TeCls in Inorganic Syntheses (7). Powder photographs of these crystals with
Ni-filtered Cu radiation were used to calculate accurate lattice parameters, and their densities were meas ~~r ed
pycnometrically with CCI4 a t 25 "C. The crystal dat a thus obtained are listed in Table I together with the
reported lattice parameters (3, 4), which are in good agreement with the present measurements.
Visually estimated intensity dat a were collected from a single crystal (0.39 X 0.15 X 0.08 mm) of
(NH4)zTeBrc in five layers parallel to the largest face (001) of the crystal with precession photographs taken
with Zr-filtered Mo radiation. The intensities were corrected for the Lorentz and polarization effects but
not for absorption. Because of the C L I ~ ~ C symmetry of the crystal, some of the reflections in higher layer
TABLE I
Crystal dat a for (NI-14)?TeBrG and CszTeBr6
System
Fornlula weight
a0
Cubic Cubic
643.2 572.9
10. 728f 0.003 A (present work) 10. 918f 0. 002 A (present work)
10.731 A (ref. 3) 10.919 A (ref. 4)
10. 73f 0. 02 A (ref. 5) 10. 910f 0. 005 A (ref. 6)
v 1234.7 A3 1301 5A3
Dm (pycilometric) 3. 42 f 0. 02 g CI I I - ~ 4 43f 0. @2gc 1n- ~
z 4 4
Dz 3. 46 g CIII-~ 4. 45 g cm-3
Absorption coefficient for Mo I<, 230 cn-I 274 cm-1
Space group Fm31)z (0;) Fna3nz(Oj)
Systematic absences hkl: hf k, kf l , h+l = 2 n f l (both crystals)
Canadian Journal of Chemlstry. Volume 44 (19GG)
939
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940 CANADIAN JOURNAL OF CHEMISTRY. VOL. 44. 1966
lines were equivalent to those in lower layers and thus the dat a from different layers c o ~ ~ l d be scaled to each
other. However, it was not possible t o scale odd and even layers together. We assumed t hat the crystal has
the K2PtC16 structure (2) and refined the positional coordinate of the bromine atom and, the a~lisotropic
temperature factors of all atoms in the n nit cell by a full matrix least-squares analysis* of the three dimen-
sional data. Each reflectio~l was weighted individually according to an estimate of its reliability. The atomic
scattering factors for all the atoms except hydrogen, which was not included in the refinement, were taken
from International Tables (8). The observed and calculated s t r ~~c t ur e factors are given in Table 11 and t he
atomic parameters after the final cycle of refinement are listed in Table IV. The weighted R index given by
R = ( Z w(lF01 - lFc1)2/ Z w I F o I ~ ) ~ ' ~
for these parameters was 0.079.
TABLE 11
The observed and calculated structure factors for (NH4)zTeBrc
h k 1 IF01 Fc h k 1 Fol Fc
*Unobservable on the precession films because of beam stop.
*The program used was written i n this laboratory by Mr. J. S. Stephens.
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DAS AND BROWN: REFI NEMENT OF CRYSTAL STRUCTURES OF (NH4)zTeBrb AND CszTeBra 941
TABLE 111
The observed and calculated structure factors for CszTeBrG
A similar procedure was followed in the refinement of the s t r ~ ~ c t ~ ~ r e of CsrTeBrs. The crystal used had
the dimensions 0.23 X 0.15 X 0.06 mm. Integrated precession photographs were taken in f o ~ ~ r layers
parallel to the largest face (011) of the crystal and the intetlsity of each reflection was measured with a
microdensitolneter. After refinement of t he structural paratneters, the weighted R index was 0.082. Table
I11 lists the observed and calculated structure factors and Table IV the final positional coordinates and
anisotropic t emper at ~~r e factors of CsrTeBrG.
TABLE IV
Xtoniic parameters derived fro111 the final least-squares refinement
Atom Positional coordinates Temperature factor*
(NHI)?TeBrG crystal
Te in 4( a) t (0,0,0; etc.) (311(=/32:!=/333) = 4 2 f 1
Br in 24(e) (x,0,0; etc.) with s = 0. 2499f 0. 0002 /311=371'3; /3??(=/333) =134f 1
N in S(c) (+ ~~I~~ '1. 7 etc.1 /311(=/32r=/333) =1 1 8 f 22
CslTeBrG crystal
Te i n 4(n) (0,0,0 ; etc.) / 311( =/ 3??=/ 3~~) =69f 4
Br i n 24(e) (x,O,O; etc.) with R. = 0. 246Sf 0.0004$ /311=53f 7; /3r?(=(333)=106+1
CS in 8(c) (,I. ,,, I ,,, t . etc.) a l l = (/32?=/333)=94f:3
*The anisotropic temperature factors appear in the structure factor calculation as esp ( - ~O-((BLIA? + p??k? + p~~l : ) ) .
+See Irlternational Tables for X-ray crystallograpll). 1'01. I, 1962. p. 338.
%The value of x g i ~ e n by Bagnalld nl . (6) isO.2-l.
RESIJLTS AND DISCIJSSIOY
Both crystals possess t he KZPtClG structure ~vhi c h is based on a face-centered cubic
array of t he octahedral TeBrG2- ions oriented with t he Te-Br bonds along the principal
cube axes. The cations occupy t he tetrahedral holes between 4 neighboring anions and are
surrounded by 12 bromine atoms, 3 f r o i n each anion.
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942 CANADIAN JOURNAL OF CHEMISTRY. VOL. 44. 1966
The Te-Br bond lengths are given in Table V. A correction can be made for the
apparent shortening of the bond due to thermal motion (9) on the assumption t hat the
TeBre2- ion is librating about the central tellurium atom. If this is done, t he mean Te-Br
bond length in both crystals becomes 2.70 A. Owing t o the uncertainty in the absolute
values of the amplitudes of thermal motion and the proper way t o correct for them, t he
standard error in this bond distance is estimated t o be about 0.01 A. Thus, the Te-Br
bond is not significantly different in two structures nor does i t differ significantly froin
the value (2.71 A) found in KzTeBr6 (1). I t is apparent t hat the cations do not have a
large influence on the structure of the anion.
TABLE V
Interatomic distances and thermal motions in MzTeBrG crystals
KzTeBrG* (NH4)2TeBr6 Cs2TeBr~
Interatomic distances before correction for thermal motion (A)
Te- Br 2.692fO.006t 2. 681f 0.00'2t 2. 695f O.004t
M-Br 3.793+0.001t 3.860+0.001t
Br-Br (between anions) 3.794+0.003t 3.909+0.003t
Interatomic distances after cor r ect i o~~ for thermal motion (see text) (A)
Te- Br 2. 71f0. 01f 2. 70f0. 01f 2.70f0.01$'
M-Br 3. 82f0. 01f 3.89+0.01$'
Br-Br (between anions) 3.S4+0.Olf 3. 94f0. 01f
Root mean square amplitudes of thermal vibration (A)
Te 0.152
Br (i) along TeBr bond 0.145 0.15 0.18
Br (ii) perpendicular to Te- Br bond 0.258 0.28 0.25
M 0.285 0.26 0.23
Ratio of perpendicular: parallel
motion of the bromineatom 1. 8 1.9 1. 4
FIG. 1. Sections through the cation perpendicular to ( I l l ) direction in ( a) CszTeBrGand (b) (StI.,)?TeBrG:
cation (striped circle), bromitie (open circle).
The thermal corrections applied t o the other interatomic distances are made on the
assuillption t hat there is no correlation between their motions. I t is interesting t o compare
the brominecation distances with those predicted from the ionic radii.* The observed
*The valzces of the ionic radii used are: Br, 2.10 2; Cs, 1.80 (Paul i ng' s rndii corrected for 12 coordinatio?~
(10)); and NH4, 1.56 A ( 1 ) (front Paztling's value of the ionic radizrs of r7~bidizcnt (1.60 11) redz~ced i n accordance
with the observation t l at crystals of (YH4)2MXt ( X = C1, Br) all Itme sliglttly smaller cells tlza?~ the correspo?tdi~zg
rubidilcm compozcnds).
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DAS AND BROWN: REFINEMENT OF CRYSTAL STRUCTURES OF (NHSzTeBre AND CstTeBrs 943
Cs-Br distance (3.89 A) is the same as t hat predicted (3.90 A) but the NH4-Br distance
(3.82 A) is considerably longer than expected (3.66 A). On the other hand, the Br-Br
separation between anions, which one inight expect to be the same in both crystals, is
shorter in (NH4)?TeBrG (3.84 A) than in CszTeBrG (3.94 A). I n the latter case, the dis-
tances are determined by the fact t hat the cesium and bromine atoms are in contact so
t hat the anions are just separated (Fig. l a). In (NH4)2TeBr6 i t is the bromine atoms in
different anions t hat are in contact (Fig. lb). The ammonium ion is smaller than the
cavity which is formed by the 12 bromine atoms which surround i t , and, as discussed in
a previous paper (I), this should lead t o a distortion a t low temperatures. At -52 OC,
(NH4)?TeBr6 transforms to a lower symmetry ( l l ) , which is probably tetragonal. A
mechanism for such a distortion has been proposed by fillorfee et al. (12) for the analogous
(NH4)2SnBr6 compound. The anions rotate about the (001) direction with alternate
anions rotating in an opposite sense. Such a rotation, which has the effect of reducing the
anion-cation separation, has been found a t room temperature in KzSnBr6 (13) and
K2TeBr6 (1). At temperatures close to the transition tenlperature, t he TeBrG2- ions would
be expected t o be librating with a rather large amplitude. This would be manifested in t he
X-ray investigation as an anisotropy in the thermal motions of the bro~nine atoms. Such
an anisotropy is indeed observed in I<?TeBrG and (NH4)zTeBrG (Table V). I t is significant
t hat although the same anisotropy is also present in CszTeBrG, i t is very much less marked.
We are presently continuing this work b>. investigating the changes which occur in
(NH ,)?TeBrG below room temperature.
ACKNOWLEDGMENTS
We acknowledge the financial support of the National Research Council of Canada
for this n.ork. One of us (A. K. D.) wishes t o thank the University of Ranchi, Bihar, India,
for granting him leave of absence.
REFERENCES
1. I. D. BROWN. Can. J. Chem. 42, 2758 (1964).
2. F. J. EWING and L. PAULING. Z. Icrist. 68, 223 (1928).
3. H. E. SWANSOY, N. T. GILFRICH, M. I. COOK, R. STINCHFIELD, and P. C. PARKS. Diffraction powder
patterns. Natl. Bur. Std. (U.S.) Circ. No. 539. 8, 1957. p. 5.
4. H. E. SWANSON, M. I. COOK, T. ISSACS, and E. H. EVANS. Diffraction powder patterns. Natl. Bur.
Std. (U.S.) Circ. No. 539. 9, 1960. p. 24.
5. L. M. MANOJLOVIC. Bull. Inst, Nucl, Sci. "Boris Kidrich" Belgrade, 7, 79 (1957).
6. I<. W. BAGNALL, R. W. M. D' EYE, and J. H. FREEMAN. J. Chem. Soc. 3963 (1955).
7. W. C. FERNELIUS. Inorganic syntheses. Vol. 2. McGraw-Hill, New York. 1946. p. 189.
8. ISTERXATIONAL TABLES FOR X-RAY CRYSTALLOGRAPHY. VOI. 111. The Icynoch Press. Birmingham,
England. 1962. Tables 3.3.1A and 3.3.1B.
9. W. R. BUSING and H. A. LEVY. Acta Cryst. 17, 142 (1964).
10. L. PAULING. The nature of the chemlcal bond. 3rd ed. Cornell University Press, New York. 1960.
pp. 511-530.
11. D. NAICAMURA, I<. ITO, and M. ICuno. J. A I ~ . Chern. Soc. 84, 163 (1982).
12. R. G. S. MORFEE, L. A. I<. STAVELEY, S. T. WALTERS, and D. L. WIGLEY. Phys. Chern. Solids, 13,
132 (1960).
13. G. MARKSTEIN and H. NOWOTNY. Z. Icrist. 100, 265 (1939). C
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