SILVER(I) CLUSTERS OF THE STERICALLY-HINDERED BIDENTATE LIGAND, 3-(DIMETHYLPHENYL)SILYL-2-PYRIDINETHIOL - THE CRYSTAL AND MOLECULAR-STRUCTURES OF [AG(SC5H3N-3-SIME2PH)]6 AND [AG8(SC5H3N-3-SIME2PH)6][AG(NO3)2]2.2CH3OH.CH2CL2

Title full: Silver(I) clusters of the sterically-hindered bidentate ligand, 3-(dimethylphenyl)silyl-2-pyridinethiol. The crystal and molecular structures of [Ag(SC5H3N-3-SiMe2,Ph)]6 and [Ag8(SC5H3N-3-SiMe2Ph)6 ][Ag(NO3)2]2·2CH3 OH·CH2Cl2. The reaction of Ag(NO3) with excess HSC5H3N-3-SiMe2Ph yields the hexanuclear [Ag6(SC5H3N-3-SiMe2Ph)6 ], a species exhibiting a molecular "paddlewheel" structure with a central Ag6S6 drum. In contrast, the reaction of excess Ag(NO3) with HSC5H3N-3-SiMe2Ph under otherwise identical conditions produces [Ag8(SC5H3N-3-SiMe2Ph)6 ][Ag(NO3)2]2·2CH3 OH·CH2Cl2. The eight silver centres of the [Ag8(SR)6]2+ central core exhibit hexagonal bipyramidal geometry, with the two silver ions of the [Ag(NO3)2]- units associated as two weakly interacting appendages. Crystal data [Ag6(SC5H3N-3-SiMe2Ph)6 ]: orthorhombic Pbca, a = 17.576(3), b = 18.634(3), c = 25.845(6) Å, V = 8464.4(11) Å3, Z = 4, Dcalc, = 1.66 g cm-3; structure solution and refinement based on 2945 reflections (Mo-Kα, λ = 0.71073 Å) converged at R = 0.0420. [Ag8(SC5H3N-3-SiMe2Ph)6 ][Ag(NO3)2]2: triclinic P1, a = 13.103(3), b = 14.766(3), c = 15.600(3) Å, α = 63.88(1), β = 80.27(2), γ = 72.35(1)°, V = 2580.5(9) Å3, Z = 1, Dcalc = 1.95 g cm-3; 5251 reflections, R = 0.0392. © 1990.