Bi53+‐Polykationen in geordneten und plastischen Kristallen von Bi5[AlI4]3 und Bi5[AlBr4]3
Bi53+‐Polykationen in geordneten und plastischen Kristallen von Bi5[AlI4]3 und Bi5[AlBr4]3
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Bi53+‐Geordneten 和塑料 Kristallen von Bi5[AlI4]3 和 Bi5[AlBr4]3 中的聚阳离子
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发表时间：
2007
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通讯作者：
Folker Steden
中科院分区：
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作者：
M. Ruck;Folker Steden
Bi_（53）+多阳离子在有序和塑性晶体Bi_（5 [AlI_4]_3）和Bi_（5 [AlBr_4]_3）中的存在
从Bi、BiX_3和AlX_3（X = Br，I）熔体中结晶出暗红色的五铋-三（四溴铝酸盐）Bi_5 [AlBr_4]_3气敏晶体和黑色的Bi_5 [AlI_4]_3气敏晶体。Bi 5 [Al I4]3单晶的X射线衍射（T = 293（2）K;空间群Pnma; a = 2143.6（3）pm，B = 1889.1（1）pm，c = 811.74（5）pm）显示了Bi 53+三角双锥和[Al I4]−四面体的有序堆积，对应于PuBr 3结构类型。与目前已知的具有精确D3 h对称性的Bi 53+聚阳离子相反，在Bi 5 [Al I 4]3中发现的铋簇仅具有Cs对称性。四溴铝酸盐Bi 5 [AlBr 4]3的室温结构与AuCu 3型有关，显示出Bi 53+聚阳离子的动态无序（T = 293（2）K;空间群; a = 1766.2（3）pm）。稍微冷却诱导转变成有序的菱面体相，与Bi 5 [AlCl 4]3同构（T = 260（2）K;空间群a = 1241.5（8）pm，c = 3041（2）pm）。
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 ; 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 a = 1241.5(8) pm, c = 3041(2) pm).