Tuning the framework formation of silver(I) coordination architectures with heterocyclic thioethers

The reactions of a series of nitrogen-containing heterocyclic thioether ligands, 2,2'-[methylenebis(thio)]bis(pyrimidine) (L-1), 2,2'-[1,2-ethanediylbis(thio)]bis(pyrimidine) (L-2), 2,2'-[methylenebis(thio)]bis[5-methyl-1,3,4-thiadiazole] (L) and 2,2'-[1,2-ethanediylbis(thio)]bis[5-methyl-1,3,4-thiadiazole] (L-4), with silver(I) nitrate or silver(I) perchlorate salt led to the formation of five new metal-organic supramolecular architectures from dinuclear to three-dimensional structures. All the structures were determined by single-crystal X-ray diffraction analysis. In the crystal structures of the five complexes, a variety of coordination modes of Ag-I have been observed, probably due to the variation of the chain length of the linker unit or the terminal groups as well as the counter anions, which indicates that the nature of the ligands is a determining factor in controlling the structural topologies of such metal-organic supramolecular architectures. Geometrical effects seem to be more important than electronic effects in these systems, leading the Ag-I centre to prefer to coordinate to N donors first rather than S donors despite Ag-I being a 'soft' metal.