PREPARATION AND REACTIVITY OF PLANAR TRIGONAL COPPER(I) COMPOUNDS - CRYSTAL-STRUCTURE OF BIS(2-THIOXOHEXAMETHYLENEIMINE)COPPER(I) BROMIDE

The crystal and molecular structure of bis(2-thioxohexamethyleneimine)copper(I) bromide, Cu(tc]H)2Br, is reported. The compound is a three-coordinate monomer and crystallizes in space group P2(1)/n with a=8.807(1), b=15.893(1), c=12.385(1) angstrom, beta=105.98(1)degrees and Z=4. It is symmetrically folded with respect to the Cu-Br bond, the copper atom being slightly elevated (0.036 angstrom) relative to the plane defined by the two sulfur and one bromine donor atoms. The two equivalent Cu-S bonds are 2.228(2) angstrom and the Cu-Br bond distance is 2.385(1) angstrom, the interbond angles around copper being close to 120-degrees. Its reactivity towards small molecules (e.g., CS2, CO2) and Lewis bases (e.g., pyridine, PPh3, AsPh3), has also been investigated.