Bi53+‐Polykationen in geordneten und plastischen Kristallen von Bi5[AlI4]3 und Bi5[AlBr4]3

Bi53+ Polycations in Ordered and Plastic Crystals of Bi5[AlI4]3 and Bi5[AlBr4]3 Dark‐red air‐sensitive crystals of pentabismuth‐tris(tetrabromoaluminate) Bi5[AlBr4]3 and black crystals of Bi5[AlI4]3 have been crystallized from melts of Bi, BiX3 and AlX3 (X = Br, I). X‐ray diffraction on a single crystal of Bi5[AlI4]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 Bi53+ trigonal bipyramids and [AlI4]− tetrahedra that corresponds to the PuBr3 structure type. Contrary to the so far known Bi53+ polycations with accurate D3h symmetry, the bismuth cluster found in Bi5[AlI4]3 holds only Cs symmetry. The room temperature structure of the tetrabromoaluminate Bi5[AlBr4]3, which is related to the AuCu3 type, shows a dynamic disorder of the Bi53+ polycations (T = 293(2) K; space group Fm 3c ; a = 1766.2(3) pm). Slight cooling induces the transition into an ordered rhombohedral phase isostructural to Bi5[AlCl4]3 (T = 260(2) K; space group R 3c a = 1241.5(8) pm, c = 3041(2) pm).