The role of the metal connectors AgNO3, Cu2I2 and CuCl2 in co-ordination-polymer formation using the N2S2 ditopic ligand 1,4-bis(2-pyridylmethylsulfanylmethyl)benzene

The extended-reach ligand 1,4-bis(2-pyridylmethylsulfanylmethyl)benzene (L) was prepared by base coupling of 2-(chloromethyl)pyridinehydrochloride and 1,4-bis(sulfanylmethyl)benzene. This new ligand was treated with metal con nectors AgNO3, CuX (X = Cl, Br or I) and CuCl2 to give co-ordination polyme rs. The crystal structures of [Ag-2(L)(NO3)(2)](infinity), [Cu-2(L)I-2](inf inity) and [Cu(L)Cl-2](infinity) were determined. Comparison of the structu res showed that the anion influenced the mode of metal binding with chelati ng or bridging modes being observed. The anion also influenced the nature o f the packing, with the silver polymer forming a three-dimensional array co ntaining clathrated water ladders while the copper polymers existed as rela ted one-dimensional polymers. The remarkable feature of these structures is that while the silver polymer showed extensive intermolecular interactions , the copper polymers, despite the prevalence of aromatic rings, each displ ayed only one type of CH/pi interaction.