TRANSITION-METAL COMPLEXES WITH SULFUR LIGANDS .79. CROWN THIOETHER COMPLEXES OF IRON, COBALT, NICKEL AND COPPER WITH BZO2-18S6 - X-RAY STRUCTURE-ANALYSIS OF [NI(BZO2-18S6)][B(C6H5)4]2 (BZO2-18S6=2,3,11,12-DIBENZO-1,4,7,10,13,16-HEXATHIACYCLOOCTADECA-2,11-DIENE)

Reaction of bzo2.18S6 (2,3,11,12-dibenzo-1,4,7,10,13,16-hexathiacyclooctadeca-2,11-diene) with Fe, Co, Ni and Cu salts yields the corresponding metal complexes [M(bzo2-18S6)]n+. Their trifluoromethanesulfonate salts were characterized by spectroscopic and electrochemical methods and the structure of [Ni(bzo2-18S6)][B(C6H5)4]2 was elucidated by X-ray structure determination. It crystallizes in space group P2(1)/n with a = 1497.8(4), b = 1096.5(4), c = 1772.5(5) pm, beta = 104.26(2)-degrees, Z = 2 and D(calc) = 1.36 g/cm3; R = 0.061, R(w) = 0.041. The nickel centre is surrounded by the six sulfur atoms of the ligand in a slightly distorted octahedron. The Ni-S distances indicate a ligand compression effect of bzo2-18S6. The different electrochemical behaviour of the [M(bzo2-18S6)]n+ complexes is discussed.