Structural isomers of octahedral M6S12 clusters formed from dithiolates. An octahedral hexasilver(I) cluster containing dialkyl dithiophosphate ligands, {Ag[S2P(OC3H7)(2)]}(6), with a different geometrical arrangement from that of {Cu[S2P(OC2H5)(2)]}(6)

The single crystal structure of {Ag[S2P(OC3H7)2]}(6), Ag6DDP6, 1, is reported. The silver atoms, each of which is trigonally coordinated to three sulfur atoms of the diisopropyl-dithiophosphate ligands, are located at the vertices of a distorted octahedron. The Ag6DDP6 molecular arrangement is different from the structure of Cu6DDP6 which has a molecular S-6 symmetry. The displacements of the silver atoms from the plane through the sulfur atoms range from 0.328(1) to 0.392(8) Angstrom. The Ag-S distances range from 2.485(2) to 2.572(2) Angstrom. The ligands occupy six of the eight faces of the Ag-6 octahedron with bridging mu(2)-S and terminal mu(1)-S coordination in an idealized D-3d symmetry. The bridging S atoms in 1 occupy the six edges of two triangular faces on opposite sides of the octahedron while in Cu-6[S2P(OC2H5)(2)](6) only terminal S atoms are on these faces. All plausible arrangements for these M6DDP6 complexes have been considered and a catalog of the surprisingly large number of distinct structures with MS3 coordinations with cis and trans uncapped faces is presented. (C) 1997 Elsevier Science Ltd.