Benzene−Copper(I) Coordination in a Bimetallic Chain Complex
- 1 December 1999
- journal article
- Published by American Chemical Society (ACS) in Inorganic Chemistry
- Vol. 38 (26) , 6200-6205
- https://doi.org/10.1021/ic991064h
Abstract
The solvothermal reaction of CuCl and ZrCl4 in benzene yields ((bz)CuCl3)2Zr (1) (bz = η2-benzene), which has been characterized by single-crystal X-ray diffraction with a = 6.1206(4) Å, b = 11.1242(4) Å, c = 13.6222(6) Å, β = 93.675(3)° in the monoclinic space group P21/m, Z = 2. 1 adopts a one-dimensional chain structure constructed from zirconium chloride octahedra and [(bz)CuCl3]2- tetrahedra. The [(bz)CuCl3]2- units are shown to be metal halide analogues of the phosphonate unit [RPO3]2-. Interchain interactions link chains of 1 along the crystallographic c direction via an edge-to-face π-stacking of the coordinated benzene molecules. The crystal packing forces influence dramatic second-order Jahn−Teller distortions, making each of the two ((bz)CuCl3)2- units distinct. These interactions further result in ligand-to-metal and metal-to-ligand charge transfers that cause an activation of the benzene ligands.Keywords
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