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Z. Kristallogr. NCS 219 (2004) 203-204 © by Oldenbourg Wissenschaftsverlag, München
Crystal structure of potassium bismuth dichloride sulfate, KBiCl2S04 M. Khelifi*1, M. Loukil'11, A. Kabadou1, R. Zouari1, A. Ben Salah1 and H. Fuess11 ' Faculté des sciences de Sfax, Laboratoire des Sciences des Matériaux et d'Environnement, Sfax, 3018 Tunisie " University of Technology, Institute for Materials Science, Petersenstrasse 23, 64287 Darmstadt, Germany Received February 16, 2004, accepted after major revision and available on-line June 23, 2004; CSD no. 409773
Discussion In the crystal structure of KBiChSCU each Bi atom is surrounded by two chlorine atoms and three oxygen atoms forming a defect octahedron (including the lone pair). Each of the oxygen atoms connects the Bi polyhedron to the sulfate tetrahedrons. Three oxygen atoms of the sulfate groups are shared with the three nearest Bi polyhedron. Then, the alternately connected Bi polyhedrons and sulfate groups form infinite double connected rows along the a axis. This structural feature affects the cell parameter. The bismuth polyhedron is based on one chlorine and three oxygen atoms. The Cll chlorine atom locates at the summit of the distorted polyhedron. The Bi—CI distances between 2.489(2) A and 2.571(2) A are shorter than those in the (NH)4BiCl6, CsK^BiCk and K4Bi2Clio • 4H2O [1-3]. The B—O distances are from 2.346(5) A to 2.622(6) A . The CI 1-Bi-O and Cll-Bi-C12 angles vary from 80.6(1)° to 92.04(7)°. The S—O distances and the O - S - O angles of the sulfate anion are close to those observed in the K 2 S0 4 (SbF 3 )2 [4] and K2SC>4SbF3 [5]. The potassium atoms are nine-fold coordinated with the neighboring chlorine and oxygen atoms. The K—CI distances vary from 3.234(3) A to 3.579(3) A , the K—O distances are from 2.779(6) A to 3.212(6) A .
Table 1. Data collection and handling.
Abstract BiCl 2 K0 4 S, orthorhombic, P2i2i2i (no. 19), a = 6.3814(6) A , ¿ = 7.3111(6) A , c = 15.367(1) A , V=717.0 A 3 , Z = 4, Rst(F) = 0.030, wRnftF2) = 0.061, T= 293 K.
Source of material A solution of (Bi0) 2 C03 was prepared in concentrated chloride acid, then mixed to a KC1 and H2SC>4 solutions with the molar ratio 0.5:1:1. By slow evaporation at room temperature, bright yellow crystals grew within several days.
Crystal: Wavelength: ff
Diffractometer, scan mode: 20m«: Wli/Jmeasured, N(7lWVique: Criterion for /obs, N(hkl)gc. N(param)refined: Programs:
colorless needle, size 0.08 x 0.08 x 0.28 mm Mo K„ radiation (0.71073 Â) 261.48 cm"1 Oxford Diffraction Xcalibur CCD, m 59.98° 5296, 1950 /obs > 2 af/obsj, 1754 82 SHELXS-97 [6], SHELXL-97 [7], DIAMOND [8]
Table 2. Atomic coordinates and displacement parameters (in Â2). Atom
Site
Bi(l) K(l) Cl(l) Cl(2) S(l) O(l) 0(2) 0(3) 0(4)
4a 4a 4a 4a 4a 4a 4a 4a 4a
1.01434(4) 0.4707(4) 0.9324(3) 1.1017(3) 1.0064(2) 0.8556(8) 1.1548(7) 1.1316(9) 0.8818(8)
0.63615(4) 1.2029(3) 0.3320(3) 0.4935(3) 0.8165(2) 0.9631(8) 0.8985(9) 0.7520(9) 0.6704(8)
0.61643(2) 0.6571(2) 0.5522(2) 0.7650(2) 0.3873(1) 0.4151(4) 0.3234(4) 0.4625(4) 0.3476(5)
Un
U22
Uiî
0.0131(1) 0.068(1) 0.035(1) 0.032(1) 0.0124(7) 0.015(2) 0.015(2) 0.023(3) 0.021(2)
0.0192(1) 0.0253(8) 0.028(1) 0.031(1) 0.0205(8) 0.019(3) 0.035(4) 0.041(4) 0.019(3)
0.0186(1) 0.030(1) 0.032(1) 0.025(1) 0.0168(8) 0.032(4) 0.028(4) 0.027(4) 0.046(4)
* Correspondence author (e-mail:
[email protected])
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U12 -0.0001(1) 0.006(1) -0.0066(9) -0.0028(9) -0.0004(7) 0.001(2) 0.001(3) 0.001(3) -0.003(2)
U13 -0.0001(1) 0.003(1) 0.0035(9) -0.0060(9) -0.001(1) 0.003(2) 0.001(2) -0.003(3) -0.001(3)
Un
0.0011(1) 0.0049(9) -0.008(1) 0.009(1) 0.0029(7) -0.003(3) 0.001(3) 0.020(3) -0.007(3)
204
KBÍCI2SO4
Acknowledgment. M. Loukil gratefully acknowledges the financial support by the Deutscher Akademischer Austausch Dienst (DAAD).
References 1. Belkyal, I.; Mokhlisse, R.; Tanouti, B.; Hesse, K.-F.; Depmeier, W.: Crystal Stucture of (NliOsBiCI«. Eur. J. Sol. State Inorg. Chem. 34 (1997) 1085-1091. 2. Benachenhou, F.; Mairesse, G.; Nowogrocki, G.; Thomas, D.: Structural studies of Cs-K-Bi mixed chlorides relation to the crystal structures of A2BMX6, AjMXé and A2MX6. J. Solid State Chem. 65 (1986) 13-26. 3. Volkova, L. M.; Udovenko, A. A.; Levin, A. N.; Schevchenko, U. Y.: The crystal structure of potssium pentachlorobismuthate dihydrate K4BÍ2CI10 - 4HjO and the comparison of the stereochemical activity of undivided electron pairs of Sb(m) and Bi(m). Coord. Chem. Rev. 9 (1983) 356-360. 4. Bourgault, M.; Ducourant, B.; Bonnet, B.; Fourcade, R.: Potassium sulphate bis(antimony fluoride) K2S04(SbF3h. J- Solid State Chem. 36 (1981) 183-189.
5. Birchall, T.; Ducourant. B.; Fourcade, R.; Mascherpa. G.: Complex formation between antimony trifluoride and alkali-metal sulphates. The Xray crystal structure of K2SO,»SbF3 and antimony-121 Moessbauer studies of some related compounds. J. Chem. Soc., Dalton Trans. (1982) 23132316. 6. Sheldrick, G. M.: SHELXS-97. Program for the Solution of Crystal Structures. University of Göttingen, Germany 1997. 7. Sheldrick, G. M.: SHELXL-97. Program for the Refinement of Crystal Structures. University of Göttingen, Germany 1997. 8. Brandenburg, K.: DIAMOND. Visual Crystal Structure Information System. Version 2. le. Crystal Impact GbR, Bonn, Germany 2000.
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