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μ(3)-十二钨(V,VI)铝酸根-κO:O':O''-三-[水合双-(乙二胺-κN,N')铜(II)]

μ(3)-Dodeca-tungsto(V,VI)aluminato-κO:O':O''-tris-[aqua-bis-(ethyl-ene-diamine-κN,N')copper(II)].

作者信息

Lu Yu-Kun, Qu Yuan-Yuan, Tian Ming-Ming, Diao Cheng-Lin, Liu Yun-Qi

出版信息

Acta Crystallogr Sect E Struct Rep Online. 2011 Dec 1;67(Pt 12):m1778-9. doi: 10.1107/S1600536811048288. Epub 2011 Nov 19.

Abstract

The title compound, [AlCu(3)W(12)O(40)(C(2)H(8)N(2))(6)(H(2)O)(3)], was prepared under hydro-thermal conditions. The Cu(2+) ion displays an elongated octa-hedral geometry defined by one bridging O atom from the polyoxidoanion and a coordinated water mol-ecule in axial positions and four N atoms of the two chelating ethyl-enediamine (en) ligands in equatorial positions. The one-electron reduced AlW(12)O(40) anion coordinates three Cu(en)(H(2)O) fragments, generating a neutral tri-supported Keggin-type polyoxidometalate (POM). This tri-supported POM is located in a special position of [Formula: see text] symmetry and therefore O atoms from the central AlO(4) tetra-hedron are disordered over two sets of sites. Disorder is also observed for three other bridging O atoms of the POM. In the crystal, mol-ecules are connected via N-H⋯O and O-H⋯O hydrogen bonds, forming a three-dimensional framework.

摘要

标题化合物[AlCu₃W₁₂O₄₀(C₂H₈N₂)₆(H₂O)₃]是在水热条件下制备的。Cu²⁺离子呈现出拉长的八面体几何构型,由来自多氧阴离子的一个桥连O原子和轴向位置的一个配位水分子以及赤道位置两个螯合乙二胺(en)配体的四个N原子所定义。单电子还原的[AlW₁₂O₄₀]⁶⁻阴离子配位三个[Cu(en)(H₂O)]²⁺片段,生成一个中性的三支撑Keggin型多金属氧酸盐(POM)。这个三支撑的POM位于[化学式:见正文]对称的一个特殊位置,因此来自中心AlO₄四面体的O原子在两组位置上无序分布。POM的另外三个桥连O原子也观察到无序。在晶体中,分子通过N—H⋯O和O—H⋯O氢键相连,形成三维框架。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7dbb/3238692/7bf55061afcb/e-67-m1778-fig1.jpg

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