Lu Yu-Kun, Tian Ming-Ming, Xu Shu-Gang, Lü Ren-Qing, Liu Yun-Qi
Acta Crystallogr Sect E Struct Rep Online. 2011 Dec 1;67(Pt 12):m1776-7. doi: 10.1107/S1600536811048197. Epub 2011 Nov 19.
The title compound, Co(C(2)H(8)N(2))(3)[SiMo(8)V(4)O(40)(VO)(2)]·6H(2)O, was prepared under hydro-thermal conditions. The asymmetric unit consists of a transition metal complex Co(en)(3) cation (en is ethyl-enediamine), one half of an SiMo(8)V(4)O(40)(VO)(2) heteropolyanion, two solvent water mol-ecules in general positions and two half-mol-ecules of water located on a mirror plane. In the complex cation, the Co(3+) ion is in a distorted octa-hedral coordination environment formed by six N atoms of the three chelating en ligands. One of the en ligands exhibits disorder of its aliphatic chain over two sets of sites of equal occupancy. The SiMo(8)V(4)O(40)(VO)(2) heteropolyanion is a four-electron reduced bivanadyl-capped α-Keggin-type molybdenum-vanadium-oxide cluster. In the crystal, it is located on a mirror plane, which results in disorder of the central tetra-hedral SiO(4) group: the O atoms of this group occupy two sets of sites related by a mirror plane. Furthermore, all of the eight μ(2)-oxide groups are also disordered over two sets of sites with equal occupancy. There are extensive inter-molecular N-H⋯O hydrogen bonds between the complex cations and inorganic polyoxidoanions, leading to a three-dimensional supra-molecular network.
标题化合物[Co(C₂H₈N₂)₃]₂[SiMo₈V₄O₄₀(VO)₂]·6H₂O是在水热条件下制备的。不对称单元由一个过渡金属配合物[Co(en)₃]³⁺阳离子(en为乙二胺)、一个[SiMo₈V₄O₄₀(VO)₂]⁶⁻杂多阴离子的一半、两个处于一般位置的溶剂水分子以及位于镜面上的两个半水分子组成。在配合物阳离子中,Co³⁺离子处于由三个螯合en配体的六个N原子形成的扭曲八面体配位环境中。其中一个en配体的脂肪链在两组占有率相等的位置上表现出无序。[SiMo₈V₄O₄₀(VO)₂]⁶⁻杂多阴离子是一种四电子还原的双钒氧基封端的α-类Keggin型钼钒氧化物簇。在晶体中,它位于镜面上,这导致中心四面体SiO₄基团无序:该基团的O原子占据由镜面相关的两组位置。此外,所有八个μ₂-氧化物基团在两组占有率相等的位置上也无序。配合物阳离子与无机多氧化阴离子之间存在广泛的分子间N-H⋯O氢键,形成三维超分子网络。