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首页> 外文期刊>Zeitschrift fur Anorganische und Allgemeine Chemie >On the crystal structures of the transition-metal(II) dodecahydro-closo-dodecaborate hydrates Cu(H2O)(5.5)[B12H12]center dot 2.5H(2)O and Zn(H2O)(6)[B12H12]center dot 6H(2)O
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On the crystal structures of the transition-metal(II) dodecahydro-closo-dodecaborate hydrates Cu(H2O)(5.5)[B12H12]center dot 2.5H(2)O and Zn(H2O)(6)[B12H12]center dot 6H(2)O

机译：过渡金属（II）十二氢-杂十二酸盐的水合物的晶体结构上Cu（H2O）（5.5）[B12H12]中心点2.5H（2）O和Zn（H2O）（6）[B12H12]中心点6H （2）

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摘要

By neutralization of an aqueous solution of the free acid (H3O)(2)[B12H12] with basic copper(II) carbonate or zinc carbonate, blue lath-shaped single crystals of the octahydrate Cu[B12H12]center dot 8H(2)O (= Cu(H2O)(5.5)[B12H12]center dot 2.5H(2)O) and colourless face-rich single crystals of the dodecahydrate Zn[B12H12] center dot 12 H2O (= Zn(H2O)(6)[B12H12]center dot 6H(2)O) could be isolated after isothermic evaporation. Copper(II) dodecahydro-closo-dodecaborate octahydrate crystallizes at room temperature in the monoclinic system with the non-centrosymmetric space group Pm (Cu(H2O)(5.5)[B12H12]center dot 2.5H(2)O: a = 768.23(5), b = 1434.48(9), c = 777.31(5) pm, beta = 90.894(6)degrees; Z = 2), whereas zinc dodecahydro-closo-dodecaborate dodecahydrate crystallizes cubic in the likewise non-centrosymmetric space group F23 (Zn(H2O)(6)[B12H12]center dot 6H(2)O: a = 1637.43(9) pm; Z = 8). The crystal Structure of Cu(H2O)(5.5)[B12H12]center dot 2.5H(2)O can be described as a rnonoclinic distortion variant of the CsCl-type arrangement. As characteristic feature the formation of isolated [Cu-2(H2O)(11)](4+) units as a condensate of two corner-linked Jahn-Teller distorted [Cu(H2O)(6)](2+) octahedra via an oxygen atom of crystal water can be considered. Since "zeolitic" water of hydratation is also present, obviously both classical H-O delta-center dot center dot center dot H+delta-O and non-classical B-H delta-center dot center dot center dot H+delta-O hydrogen bonds play a significant role for the stabilization of the structure. A direct coordinative influence of the quasi-icosahedral [B12H12](2-) anions on the Cu2+ cations has not been determined. The zinc Compound Zn(H2O)(6)[B12H12]center dot 6H(2)O crystallizesin a NaTl-type related structure. Two crystallographically different [Zn(H2O)(6)](2+) octahedra are present, which only differ in their relative orientation within the packing of the [B12H12](2-) anions. The stabilization of the crystal structure takes place mainly via H-O delta-center dot center dot center dot H+delta-O hydrogen bonds, since again the hydrogen atoms of the [B12H12](2-) anions have no direct coordinative influence on the Zn2+ cations.
机译：通过用碱式碳酸铜（II）或碳酸锌中和游离酸（H3O）（2）[B12H12]的水溶液，八水合物Cu [B12H12]中心点8H（2）O的蓝条形单晶（= Cu（H2O）（5.5）[B12H12]中心点2.5H（2）O）和十二水合物Zn [B12H12]中心点12 H2O的无色富面单晶（= Zn（H2O）（6）[B12H12等温蒸发后可以分离出[中心点6H（2）O）。在室温下，具有非中心对称空间群Pm（Cu（H2O）（5.5）[B12H12]中心点2.5H（2）O：a = 768.23（ 5），b = 1434.48（9），c = 777.31（5）pm，β= 90.894（6）度; Z = 2），而十二水合氢-十二碳杂十二酸锌十二水合物在非中心对称空间群F23中结晶为立方晶（Zn（H2O）（6）[B12H12]中心点6H（2）O：a = 1637.43（9）pm; Z = 8）。 Cu（H2O）（5.5）[B12H12]中心点2.5H（2）O的晶体结构可以描述为CsCl型排列的微斜变畸变。作为特征性特征，形成了分离的[Cu-2（H2O）（11）]（4+）单元，作为两个角连接的Jahn-Teller扭曲的[Cu（H2O）（6）]（2+）八面体的缩合物。可以考虑结晶水的氧原子。由于还存在“沸石”水化水，显然，经典的HOδ-中心点中心点中心点H + delta-O和非经典BHδ-中心点中心点中心点H + delta-O氢键都起着对于稳定结构起着重要作用。尚未确定准二十面体[B12H12]（2-）阴离子对Cu2 +阳离子的直接配位影响。锌化合物Zn（H2O）（6）[B12H12]中心点6H（2）O在NaTl型相关结构中结晶。存在两种在晶体学上不同的[Zn（H2O）（6）]（2+）八面体，它们在[B12H12]（2-）阴离子堆积中的相对取向不同。晶体结构的稳定主要通过HOδ-中心点中心点中心点H + delta-O氢键进行，因为[B12H12]（2-）阴离子的氢原子再次对Zn2 +没有直接配位影响阳离子。

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