Benzene-Copper(I) Coordination in a Bimetallic Chain Complex.
The solvothermal reaction of CuCl and ZrCl(4) in benzene yields ((bz)CuCl(3))(2)Zr (1) (bz = eta(2)-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, beta = 93.675(3) degrees in the monoclinic space group P2(1)/m, Z = 2. 1 adopts a one-dimensional chain structure constructed from zirconium chloride octahedra and [(bz)CuCl(3)](2)(-) tetrahedra. The [(bz)CuCl(3)](2)(-) units are shown to be metal halide analogues of the phosphonate unit [RPO(3)](2)(-). Interchain interactions link chains of 1 along the crystallographic c direction via an edge-to-face pi-stacking of the coordinated benzene molecules. The crystal packing forces influence dramatic second-order Jahn-Teller distortions, making each of the two ((bz)CuCl(3))(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.