Three novel structure types of polythiometalates: Syntheses, structures, and electrical properties of {[W4Ag6S16]center dot[Ca(DEAC)(6)]}(n), {[W2Ag2S8]center dot[ Zn(4,4 '-bipy)(2)(DMF)(2)(DMSO)(2)]}(n), and {[W2Ag2S8]center dot[Zn(4,4 '-bipy)(2)(DMSO)(4)]center dot(DMSO)}(n)

Three novel 1-D coordination polythiometalates have been synthesized and ch aracterized by single-crystal X-ray crystallography, and their electrical p roperties have been studied. Compound {[W4Ag6S16] . [Ca(DEAC)(6)]}(n) 1 cry stallizes in the monoclinic space group P2(1)/n with a = 13.769(3), b = 11. 613(2), c = 24.153(5) Angstrom, beta = 96.31(3)degrees, V = 3838.7(13) Angs trom, and Z = 2 with R(wR2) = 0.0607(0.1338), the polymeric anions in 1 fea ture a novel hanging ladder-like polymeric chain which can also be describe d as double helical chains bridged by silver atoms. Both compounds {[W2Ag2S 8] . [Zn(4,4'-bipy)(2)(DMF)(2)(DMSO)(2)]}(n) 2 and {[W2Ag2S8] . [Zn(4,4'-bi py)(2)(DMSO)(4)] . (DMSO)}(n) 3 are composite polymers which consist of pol ymeric cations as well as polymeric anions, In 2, two polymeric chains simu ltaneously exist in the cell unit, one is the zigzag anionic chain, the oth er is the linear cationic chain. 2 crystallizes in the monoclinic space gro up C2/c with a = 8.996(2) Angstrom, b = 21.728(4) Angstrom, c = 21.560(4) A ngstrom, beta = 94.00(3)degrees, V = 4204(2) Angstrom(3), and Z = 8 with R( wR2) = 0.0546(0.1556), The difference between 2 and 3 is that the latter ha s a linear anionic chain and a zigzag cationic chain. X-ray crystallography established the monoclinic space group C2/c with a = 28.8896(2), b = 11.93 95(1), c = 16.2341(2) Angstrom, beta = 122.932(1)degrees, V = 4699.82(8) An gstrom(3), and Z = 8 with R(wR(2)) = 0.0438(0.1166) . 4.50 x 10(-6) S cm(-1 ), respectively. Room temperature conductivities of 1, 2 are 2.92 x 10(-5). Thus, compounds 1 and 2 have semiconductor electrical properties. (C) 2000 Academic Press.