Reaction of copper(l) iodide with pyridine-2-thione (2-SC5H4NH) and 1,2-bis(diphenylphosphino)ethane (dppe) in a CH3CN-CHCl3 mixture yielded a triangular cluster, [Cu3I3(mu(2)-P,P-dppe)(3)(eta(1)-SC5H4NH)], 1. Similar reaction with 2-SC5H4NH and a series of diphosphanes, Ph2P-X-Ph2P {X = -CH2- (dppm), -(CH2)(3)- (dppp), -(CH2)(4)- (dppb), -CH=CH- (dppen)}, gave a novel iodo-bridged hexanuclear Cu-l linear polymer, {Cu-6(mu(3)-SC5H4NH)(4)(mu(2)-SC5H4NH)(2)(l(4))(mu-l)(2-)}(eta)(.)2nCH(3 )CN, 2. Reactions of copper(l) iodide/copper(l) bromide with 1,3-imidazolidine-2-thione (SC3H6N2) in a CH3CN-CHCl3 mixture yielded hexanuclear Cu-l linear chain polymers, [{Cu-6(mu(3)-SC3H6N2)(2)(mu(2)-SC3H6N2)(4)X-2-(mu-X-4}(eta)] (X = Br, 4; I, 5). In compound 1, two iodide atoms and one dppe form the clinuclear Cu(mu(2)-I)(2)(mu(2)-dppe)Cu core, and two dppe ligands bridge this core with the third Cu(l) center coordinated to 2-SC5H4NH via the S atom. The chain polymer 2 has a centrosymmetric hexanuclear central core, Cu6S6I4(mu-I)(2)-, formed by dimerization of six-membered trinuclear motifs, Cu-3(mu(2)-SC3H6N2)(3)](3) via (mu(3)-S) bonding modes of the thione ligand, and has four terminal and two bridging iodine atoms in trans-orientations. Linear chains are separated by the nonbonded acetonitrile molecules. In 4 and 5, three copper(l) bromide or copper(l) iodide moieties and three SC3H6N2 ligands combined via bridging S donor atoms to form the six-membered trinuclear Cu-3(mu(2)-SC3H6N2)(3)I-3 cores which polymerized via S and X atoms in a side-on fashion to form linear chain polymers, [{Cu-6(mu(3)-SC3H6N2)(2)(mu(2)-SC3H6N2)(4)X-2(mu-X)(4)}(eta)]. The (mu(3)-S) modes of bonding of neutral heterocyclic thioamides are first examples, as are trinuclear cluster and linear polymers rare examples in copper chemistry.