688 N otizen
The Crystal Structure of
Cesium Fluorotrioxosulfate(VI), C s S 0 3F Peter Rögner and Klaus-Jürgen Range*
Institute o f Inorganic Chemistry,
U niversity o f Regensburg, Universitätsstraße 31, D -W -8400 Regensburg
Z. Naturforsch. 48b, 6 8 8 -6 9 0 (1993);
received January 11, 1993 Cesium Fluorotrioxosulfate(V I), Crystal Structure
The crystal structure o f C s S 0 3F was deter
mined from single-crystal X-ray data as tetrag
onal. space group 14,/am d, with a = 5.6317(2), c = 14.1991(9) A and Z — 4. The structure was refined to R = 0.028, R w = 0.028 for 403 unique reflections.
In contrast to the earlier literature C s S 0 3F is not isom orphous with scheelite but with a -C s R e 0 4. The structure contains isolated S 0 3F tetrahedra which are linked together by twelve
fold coordinated Cs ions. The average S —0 ,F dis
tance is 1.453(3) A.
Among the fluorosulfates M 'SO jF the salts with M1 = K, N H 4, Rb crystallize in the orthorhom bic space group P nm a [1], The crystal structure was determined as the barite type for the potassium [2] and am m onium com pound [3]. Cesium fluorosul- fate, however, was found to be not isom orphous with the other alkali fluorosulfates. From powder patterns a tetragonal unit cell with cell dimensions a = 5.610(6), c = 14.133(9) Ä and c/a = 2.519(2) was assigned to C sS 03F. By an examination of the observed reflection conditions it was proposed that C sS 0 3F belongs to the scheelite type although the positions of the oxygen and fluorine atom s had not been established [1],
During our investigations on perrhenates we re
cently refined the crystal structure of a -C sR e 0 4, the high-tem perature m odification of cesium per- rhenate [4]. The lattice constants were a = 5.9607(4), c = 14.446(1) A and c/a = 2.423. In con
trast to the earlier literature, in which space group I4]/a (and therefore a scheelite type structure) was assumed for a -C sR e 0 4, we could confirm the space group 14,/amd to be the right one.
A further com pound which crystallizes in the a -C sR e 04 structure type is cesium perbrom ate,
* Reprint requests to Prof. K.-J. Range.
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C s ß r04 [5] with unit cell param eters a = 5.75, c = 14.82 A and c/a = 2.58. Though the crystal struc
ture was originally described in space group 14,/a we found that 14,/amd is appropriate for C sB r04 [6],
Regarding the similarities of C sS 03F,
<*-CsRe04 and C sB r04 with respect to the unit cell dimensions a scheelite type structure of C sS 0 3F became questionable. Since the reflection condi
tions observed by Seifert [1] were not only fulfilled in space group 14,/a, but in 14,/am d as well, we de
cided to reinvestigate the crystal structure of C sS 03F.
Cesium fluorosulfate was prepared by neutrali
zation of a m ixture of hydrofluoric acid (40% ) and oleum (60% S 0 3) with cesium carbonate. Recrys
tallization of the reaction product from water yielded single crystals of cesium sulfate and cesium fluorosulfate. Due to their different m orphology crystals o f the title com pound could be easily separated. A bipyram idal crystal of C sS 0 3F (crys- tallographic forms {1 1 2}, {1 0 1} and {0 0 1}) of about one mm in diam eter was ground to a sphere and used for the structure determ ination.
Precession photographs exhibited the Laue class 4/mmm and the reflection conditions (h k l):
h + k + l = 2«, ( h k0): h ,k = 2n and (hkl): 2h + l = 4 n which uniquely indicated the space group 14,/
amd. A scheelite type structure could therefore be excluded with certainty.
D ata collection was perform ed on an Enraf- Nonius CAD-4 diffractom eter using M o K a radia
tion (graphite m onochrom ator in incident beam).
The unit cell param eters were obtained by a least- squares refinement based on 25 carefully centred reflections in the range 13.7 < 0 < 19.0°. Three standard reflections were measured every 100 min, indicating only random fluctuations in intensity.
After reduction o f the 1534 recorded data a set of 403 independent reflections with I > 0cr(I) re
mained (R ml =0.021), of which all were used in the subsequent calculations. Crystallographic and ex
perimental d ata are summarized in Table I.
All calculations were carried out using the p ro
grams SHELX-76 [7] and SH ELX S-86 [8], Atomic scattering factors and corrections for anom alous dispersion were taken from the International Tables for X-ray Crystallography [9].
The structure was solved by Patterson m ethods, followed by successive difference Fourier syn
theses. The final full-matrix least-squares refine
ment (including anisotropic displacement factors and an extinction correction of the form F corr = Fc( l - g F2/sinö)) converged at R = 0.028 and Rw = 0.028. Atomic positions and displacement factors
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N otizen 689
Formula M olecular weight Space group Cell dimensions
Density (calcd) H (M o K a ) F(000) Temperature Radiation Scan mode Scan width 2 0 range h k l limits (s in 0 //)max
Recorded reflections U nique reflections, R mt R eflections used in
least-squares refinement Parameters refined
( ^ A 7) max
W eighting scheme Final R, /?w
ö )m a x Jmin
Extinction coefficient g
CsSOjF 231.97 g - m o r 1 14,/am d (Nr. 141) a = 5.6317(2) Ä c = 14.1991(9) Ä c/a = 2.521 V = 450.34(3) Ä 3 4
3.421 g e m -3 8.50 mm 1 416 2 9 5 (1 )K
M o K « ( x = 0.71073 Ä) c o - 2 0
(0.6 + 0.35 tan#)°
2° < 2 0 < 80°
- 1 0 < /z < 10; 0 < 10; 0 < / < 25 0.90 Ä “1
1534 403,0.021 403
13 0.002
w = 1.1164 • (er2(F 0) + 0.000007 F2) -1 0.028,0.028
+ 0.4, - 0 . 7 e Ä “3 6.0(1) • 1 0 7
Table I. Crystal data, data collection and re
finement parameters for C s S 0 3Fa.
a Here, as in the follow ing tables, the standard deviations are given in parentheses.
for CsS0 3F are given in Table II, derived atomic distances and angles in Table III*.
The results o f the structure refinement show that C sS 0 3F and a -C s R e 04 are indeed isostruc- tural. Therefore, the oxygen and fluorine atom s are statistically distributed on the 16 h site.
The structure o f C sS 0 3F consists o f isolated S 0 3F tetrahedra which are linked together by cesium ions. Cesium is twelvefold coordinated by oxygen and fluorine with an average C s - 0 , F dis
tance of^ 3.290(2) A. The S —0 , F distance of 1.453(3) A is in agreem ent with the m ean values of 1.447(3) A in C sH (S 03F)2 [10], 1.455(20) Ä in K S 0 3F [2], 1.465(4) Ä in L iS 0 3F [11], 1.466(4) Ä in N H4S 0 3F [3] and 1.473(1) Ä in H S 0 3F [12].
The generous support given by the Deutsche For
schungsgem einschaft (G raduiertenkolleg “Com plexity in Solids - Phonons, Electrons and Structures”) and the Fonds der Chemischen Industrie is gratefully acknow l
edged. We thank Dr. U . Klem ent for the collection o f diffractometer data.
* Lists o f structure factors, bond distances and bond angles have been deposited at the Fachinform ations- zentrum Karlsruhe G m bH , D -W -7514 Eggenstein- Leopoldshafen 2. Copies m ay be obtained by quoting the depository number C SD 57082, the name o f the authors and literature citation.
Table II. A tom ic positional parameters and displace
ment factores [A2] for C s S 0 3F. Fractional atom ic coor
dinates and equivalent isotropic displacem ent parame
ters3. Origin at centre (2/m).
A tom Site x/a y / b z/c u eq
Cs 4a 0
S 4b 0
0 ,F 16 h 0
3/4 1/4 0.5371(6)
1/8 3/8 0.6828(2)
0.0282(1) 0.0414(4) 0.0584(9) Anisotropic displacement factors
Atom U | , u 22 u 33 u 23
Cs 0.0285(1)
S 0.0442(5)
0 ,F 0.049(1) U ,2 = U 13 = 0
U „ U „ 0.066(2)
0.0275(2) 0.0357(7) 0.060(2)
0 0 0.037(1)
a U eq is defined as gonalized U - tensor.
one third o f the trace o f the ortho-
Table III. Selected interatomic distances [Ä] and bond angles [°],
S -O .F 1.453(3) (4 x ) 0 , F - S —0 ,F 111.3(3) (2 x ) 0 , F - 0 , F 2.359(4) (4 * ) 0 , F - S —0 ,F 108.6(1) (4 x) 0 , F - 0 , F 2.399(4) (2 x )
C s - 0 ,F 3.172(3) (4 x ) C s - S 3.982 C s - 0 ,F 3.349(3) (8 x) C s -C s , S - S 4.508
690 N o tizen
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