PREPARATION, CHARACTERIZATION AND X-RAY CRYSTAL STRUCTURES OF I-2 AND COPPER(II) COMPLEXES OF 2,11-DITHIA[3.3]PARACYCLOPHANE

摘要

The crystal structures of dtpcpI(4) (1), [CuCl2(dtpcp)(EtOH)] (2) and [CuBr2(dtpcp)(MeOH)] (3), where dtpcp = 2,11-dithia[3,3]-paracyclophane, have been determined by X-ray crystallography. Complex 1 contains two crystallographically independent I(2)dtpcpI(2) molecules in the unit cell, each having crystallographical -1(C-i) symmetry. The structures of both 2 and 3 consist of a one-dimensional array of copper(II) ions linked via dithia-bridged paracyclophane. While 1 is an electric insulator at room temperature, the iodine oxidation of 2 and 3 produced charge-transfer complexes which gave conductivities 10(-5.5) and 10(-6.9) S cm(-1), respectively. Both 2 and 3 show the typical ESR signals and normal magnetic moments for a dilute copper(II) ion at room temperature, but exhibit an antiferromagnetic coupling at low temperature through the conjugated rr system of the bridging ligand. [References: 23]