Benzene−Copper(I) Coordination in a Bimetallic Chain Complex

• Published in: Inorganic chemistry Vol. 38; no. 26; pp. 6200 - 6205
• Main Authors: Dattelbaum, Andrew M, Martin, James D
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 27-12-1999
• ISSN: 0020-1669; 1520-510X
• DOI: 10.1021/ic991064h

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.