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Bi 5 3+ ‐Polykationen in geordneten und plastischen Kristallen von Bi 5 [AlI 4 ] 3 und Bi 5 [AlBr 4 ] 3
Author(s) -
Ruck Michael,
Steden Folker
Publication year - 2007
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/zaac.200700095
Subject(s) - isostructural , crystallography , bismuth , trigonal crystal system , chemistry , crystal structure , space group , group (periodic table) , materials science , stereochemistry , diffraction , physics , x ray crystallography , optics , organic chemistry
Bi 5 3+ Polycations in Ordered and Plastic Crystals of Bi 5 [AlI 4 ] 3 and Bi 5 [AlBr 4 ] 3 Dark‐red air‐sensitive crystals of pentabismuth‐tris(tetrabromoaluminate) Bi 5 [AlBr 4 ] 3 and black crystals of Bi 5 [AlI 4 ] 3 have been crystallized from melts of Bi, Bi X 3 and Al X 3 ( X = Br, I). X‐ray diffraction on a single crystal of Bi 5 [AlI 4 ] 3 ( T = 293(2) K; space group Pnma ; a = 2143.6(3) pm, b = 1889.1(1) pm, c = 811.74(5) pm) revealed an ordered packing of Bi 5 3+ trigonal bipyramids and [AlI 4 ] − tetrahedra that corresponds to the PuBr 3 structure type. Contrary to the so far known Bi 5 3+ polycations with accurate D 3h symmetry, the bismuth cluster found in Bi 5 [AlI 4 ] 3 holds only C s symmetry. The room temperature structure of the tetrabromoaluminate Bi 5 [AlBr 4 ] 3 , which is related to the AuCu 3 type, shows a dynamic disorder of the Bi 5 3+ polycations ( T = 293(2) K; space group $Fm{\bar 3}c$ ; a = 1766.2(3) pm). Slight cooling induces the transition into an ordered rhombohedral phase isostructural to Bi 5 [AlCl 4 ] 3 ( T = 260(2) K; space group $R{\bar 3}c$ a = 1241.5(8) pm, c = 3041(2) pm).