A UNIQUE COORDINATION POLYMER CONSISTING OF 2 PARALLEL C5H4S5 MOLECULES BRIDGING 2 SILVER(I) IONS (C5H4S5 EQUALS 4,5-ETHYLENEDITHIO-1,3-DITHIOLE-2-THIONE)

The silver(I) complex with 4,5-ethylenedithio-1,3-dithiole-2-thione (C 5H4S5), [Ag(C5H4S5)(2)NO3](infinity), was synthesized and the molecula r structure and packing were characterized crystallographically. The A g atom is coordinated with four ligands through two thiocarbonyl sulfu r atoms (C = S) and two thioether sulfur atoms of the six-membered rin g (-S-), respectively, forming an extremely distorted tetrahedral geom etry. This is the first metal complex of TTF or BEDT-TTF analogs, in w hich the sulfur atom in a five- or six-membered ring directly coordina tes to the silver(I) ion. Two parallel C5H4S5 molecules are connected by two Ag(I) ions to give a unique infinite chain. The S ... S contact s of 3.41 Angstrom are very strong between two nearby chains along the b axis, generating a two-dimensional network. The crystal of the comp lex is monoclinic with space group P2/n, a = 8.701(1), b = 8.955(1), c = 11.811(1) Angstrom, beta = 91.438(8)degrees, V = 920.0 Angstrom(3), Z = 2, R = 0.031, R(w) = 0.045. Although the iodine-doped free ligand is an insulator, the iodine-doped complex is a semiconductor (sigma = 3 x 10(-5) S cm(-1)) at room temperature.