Synthesis and Crystal Structures of Rb4Al2S5 and Cs4In2S5
Synthesis and Crystal Structures of Rb4Al2S5 and Cs4In2S5
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Rb4Al2S5 和 Cs4In2S5 的合成及晶体结构
DOI：
10.1002/zaac.201400567
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发表时间：
2015
期刊：
影响因子：
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通讯作者：
A. Pfitzner
中科院分区：
文献类型：
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作者：
V. Winkler;M. Schlosser;A. Pfitzner
通过叠氮化物路线获得了两种新的碱金属硫代三醋酸盐，其一般组成为M4T2S5（M = Rb，Cs；T = Al，In），并根据单晶X射线衍射数据确定了它们的晶体结构。对空气高度敏感的 Rb4Al2S5 在空间群 Pna21（编号 33）中以浅红色棒状结晶，其晶格常数 a = 11.4450(5) A、b = 11.4605(6) A、c = 9.5727(4) A，晶胞体积为 V = 1255.6(1) A3，Z = 4。 据我们所知， Rb4Al2S5代表了第一种硫代铝酸铷，也是三元碱金属硫族金属酸盐领域的一种新结构类型。 Cs4In2S5 在空间群 P（编号 2）中与 Rb4In2S5 同型结晶，晶格常数 a = 9.6871(3) A, b = 11.1549(4) A, c = 7.7879(3) A, α = 110.731(3)°, β = 95.760(3)°, γ = 102.766(2)°，晶胞体积为 V = 752.75(4) A3，Z = 2。两种固体的晶体结构均由边缘连接的 [T2S6]6– 双四面体组成，通过跨角共享构建一维聚合 1∞[T2S54–] 链。阴离子链分别被铷和铯阳离子分开。铝和铟具有被硫包围的稍微扭曲的四面体，并且Rb4Al2S5中的四个独立的铷原子分别具有扭曲的三棱柱和扭曲的八面体配位球。在 Cs4In2S5 中，四个不同的铯位置显示配位数为六和七。 Cs4In2S5 还通过拉曼光谱进行了表征。 In-S 拉伸模式的频率范围为 342 cm-1 至 292 cm-1。
Two new alkali metal thiotrielates with the general composition M4T2S5 (M = Rb, Cs; T = Al, In) were obtained via the azide route and their crystal structures were determined from single-crystal X-ray diffraction data. Highly air sensitive Rb4Al2S5 crystallizes in pale red rods in the space group Pna21 (no. 33) with lattice constants a = 11.4450(5) A, b = 11.4605(6) A, c = 9.5727(4) A, and a cell volume of V = 1255.6(1) A3 with Z = 4. To the best of our knowledge, Rb4Al2S5 represents the first rubidium thioaluminate and a new structure type in the field of ternary alkali metal chalkogenometallates. Cs4In2S5 crystallizes isotypic to Rb4In2S5 in the space group P (no. 2) with lattice constants a = 9.6871(3) A, b = 11.1549(4) A, c = 7.7879(3) A, α = 110.731(3)°, β = 95.760(3)°, γ = 102.766(2)°, and a cell volume of V = 752.75(4) A3 with Z = 2. The crystal structures of both solids consist of edge-linked [T2S6]6– double tetrahedra, which build up one-dimensional, polymeric 1∞[T2S54–] strands by trans-corner sharing. The anionic chains are separated by rubidium and cesium cations, respectively. Aluminum as well as indium has a slightly distorted tetrahedral surrounding by sulfur, and the four independent rubidium atoms in Rb4Al2S5 feature distorted trigonal prismatic and distorted octahedral coordination spheres, respectively. In Cs4In2S5 the four different cesium positions show coordination numbers of six and seven. Cs4In2S5 was also characterized by Raman spectroscopy. The frequencies of In–S stretching modes are found in the range from 342 cm–1 to 292 cm–1.