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Two complexes, [WS4Cu5I3(bbd)2] n (1) and [(WS4Cu3I)2(bbd)3] n ·n(DMF) (2), with one-dimensional polymeric chain structures containing hexanuclear and tetranuclear clusters linked by flexible 1,4-bis(3,5-dimethylpyrazol-1-yl)butane (bbd) ligands have been synthesized in facile one-pot reactions at room temperature, together with the molybdenum analogue of 2. The only significant difference in the syntheses of the two tungsten complexes is the 5:1 or 3:1 molar ratio of copper(I) to [WS4]2–, the other experimental factors being kept constant. The observed products reflect the stoichiometric Cu:W ratio used. All three complexes were characterized by IR and UV–vis spectroscopy, thermal and elemental analyses, and single-crystal X-ray diffraction. Complex 1 contains an unusual and surprisingly unsymmetrical WS4Cu5I3 cluster in which five Cu atoms bridge all but one of the six S···S edges of the WS4 tetrahedron and the three I atoms all have different coordination modes (terminal, μ2 and μ3); it consists of two face-sharing WS3Cu3I distorted cubes, in one of which a Cu···I edge is opened up instead of being bonded, this Cu atom (shared by the two cubes) having an additional terminal iodo ligand. Complex 2 is the first reported example of a polymer containing (S=)MS3M′3X cubes linked by organic ligands; pairs of these cube clusters are connected by pairs of bbd ligands, and the (cluster)2(bbd)2 units are assembled into chains by single bbd bridges. In these and previously reported complexes, the bbd bridging ligand displays considerable flexibility, enabling it to support a range of discrete oligomeric and polymeric structures. X-ray powder diffraction shows that 2 is consistently obtained as a mixture of two polymorphs, and the same has been found for the corresponding molybdenum complex [(MoS4Cu3I)2(bbd)3] n ·n(DMF) (3), for which the second polymorph has been structurally characterized by single-crystal diffraction using synchrotron radiation. The two polymorphs have essentially identical polymer chain structures, with different packing arrangements of the chains and different symmetry properties.

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Reactions of AgI with salts of [WS(4)](2-) or [MoS(4)](2-) and with either imidazolidine-2-thione (Imt) or [1,3]diazepane-2-thione (Diap) give the complexes [WS(4)Ag(2)(Imt)(2)](n) and [MS(4)Ag(2)(Diap)(4)] [M = W or Mo]; in the case of Diap, corresponding Cu complexes can be obtained with CuCl instead of AgI. Decomposition of the Ag-Diap complexes during attempted recrystallization leads to the polymeric complex [AgI(Diap)](n). The monomeric mixed-metal Diap complexes contain edge-sharing WS(4) and AgS(4) tetrahedra, the Diap ligands being terminally bonded to Ag through sulfur. The mixed-metal W-Ag-Imt complex is a chain polymer with two different environments for the WS(4) unit and three different coordination environments for Ag, one of which is an unprecedented AgS(5) square-based pyramid; Imt ligands are terminally coordinated to Ag. [AgI(Diap)](n) has a complex polymeric chain structure with three different distorted tetrahedral environments for Ag, direct Ag-Ag bonding, both bridging and terminal I, and all Diap ligands bridging pairs of Ag atoms. All the crystal structures feature N-H[...]S or N-H[...]I hydrogen bonding. The complexes have also been characterised by infrared, UV-Vis and (1)H and (13)C NMR spectroscopy.

This work presents the synthesis of close-packed copper complexes with an uncommon ability for dye and iodine adsorption and antibacterial activities.

In the current work, we have managed to design and synthesize a set of four new sulfur coordination polymers, namely, [ZnCl2(Ls)2] n (1), [CdCl2(Ls)2] n (2), [Cd­(NCS)­(μ2-SCN)2(Ls)2] n (3), and {[Hg­(μ2-Cl)­(Ls)2]­[ClO4]} n (4) using a branch tube method. They have been fully characterized using several techniques including elemental analysis, Fourier transform infrared spectroscopy, powder X-ray diffraction, photoluminescence spectroscopy, UV–vis, and single-crystal X-ray diffraction. Polymer 1 was synthesized directly by the reaction of zinc ions with the Ls ligand, while polymer 2, which is isostructural with 1, was synthesized by a single-crystal-to-single-crystal postsynthetic modification of polymer 1 where Zn­(II) ions were substituted by Cd­(II) ions. The effect of the anion on changing the topology has been carried out in polymer 3 using a thiocyanate anion in which SCN– groups were bonded to the metal centers in both terminal and bridging coordination fashions to form a two-dimensional network structure. The competition between halogen and uncoordinated perchlorate anions along with the Ls ligand constructed a cationic one-dimensional network structure in {[Hg­(μ2-Cl)­(Ls)2]­[ClO4]} n in which halogen atoms bridged between the metal centers and perchlorates counterbalanced the charge. The title polymers were considered as iodine and H2S adsorbents, and their kinetics were studied in detail. All polymers showed extreme stability toward both pollutants, and polymer 4 removed more than 99% of I2 from the solution. The presence of halogen and ClO4 – anions in polymer 4 was the key factor for its best removal efficiency in this group.

In the title complex, [CdCl2(C4H6N2S)2], the Cd atom has a distorted tetra­hedral coordination geometry, with two Cl− and two monodentate neutral thione ligands bonded through S. There are intra­molecular N—H⋯Cl and inter­molecular N—H⋯S hydrogen bonds, generating centrosymmetric dimers.