Structural diversity in silver(I) and gold(I) complexes with 2,5-bis(diphenylphosphinomethyl)thiophene

Polynuclear silver(I) and gold(I) complexes with 2, 5-bis(diphenylphosphino methyl)thiophene (dpmt) [Ag-2(mu-dpmt)(3)][BPh4](2). 2MeCN 1, [Ag2Cl2(mu-dp mt)] 2, [Ag3Br3(mu-dpmt)(2)] 3, [Ag3I3(mu-dpmt)(2)] 4, [Au2Cl2(mu-dpmt)] 5, [Au2Cl2(mu-dpmt)(2)] 6, [Au2Cl2(mu-dpmt)(3)] 7 and [(Au2S)(mu-dpmt)] 8 wer e synthesised and 1, 4, 5 and 8 structurally characterised by X-ray crystal lography. Complex 1 consists of a binuclear triple-helical [Ag-2(mu-dpmt)(3 )] cation with two three-coordinated Ag-I bridged by three dpmt ligands in a staggered-conformation with respect to the two AgP3 moieties. Complex 4 h as a 'three-runged ladder' Ag-3(mu(3)-I)(mu-I)(2) unit which is bridged by two dpmt ligands above and below the trinuclear plane. Two of the Ag-I are tetrahedrally co-ordinated and one, in the middle of the structure unit, ha s trigonal co-ordination geometry. In 5, a pair of AuCl is bridged by one d pmt in which both Au-I exhibit linear, two co-ordinated geometry. Complex 8 has a binuclear cyclic structure with a narrow Au-S-Au angle of 86.2(1)deg rees and short Au ... Au distance of 3.131(1) Angstrom indicating a certain amount of intra-molecular Au ... Au interaction.