Polymer and cage-type structures in silver(I) complexes with heterocyclic thiones and bridging diphosphine ligands.: Crystal structures of [Ag(μ-dpppent)(tHpymtH)(ONO2)]n and [Ag2(μ-trans-dppen)3(pymtH)2](NO3)2 • CH3CN

Reaction of silver(l) nitrate with equimolar amounts of the rigid diphos ligand traps-1,2-bis(diphenylphosphino)ethene (trans-dppen) and some heterocyclic thiones (L) in acetonitrile/methanol solvent gave rise to triply-bridged coordination cages [Ag-2(mu(2)-trans-dppen)(3)L-2](NO3)(2). On the other hand, the complexes produced when using the flexible 1,5-bis(diphenylphosphino)pentane (dpppent) turned out to be diphosphine-bridged polymers of the type [Ag(mu(2)-dpppent)(L)(ONO2)](n) with the diphosphine ligand acting as bridge between two pseudo-tetrahedraly coordinated metal centres. The structures of one representative for each of the two aforementioned series of complex compounds, namely, [Ag-2(mu(2)-trans-dppen)(3)(pymtH)(2)](NO3)(2) (pymtH = pyrimidine-2-thione) and [Ag(mu(2)-dpppent)(tHpymtH) (ONO2)] (tHpytntH = tetrahydropyrimidine-2-thione) have been established by single-crystal X-ray diffraction. (c) 2005 Elsevier Ltd. All rights reserved.