Reactions of the preformed cluster precursor [Et4N]2[Mo2S2(μ-S)2(edt)2] (edt = ethanedithiolate) (1) with [Au(PPh3)Cl] in MeOH/MeCN gave rise to a new heterobimetallic Mo/Au/S cluster [Et4N][Mo2S4(AuPPh3)(edt)2]·0.25Et2O·0.25MeOH (2·0.25Et2O·0.25MeOH). It was characterized by elemental analysis, IR spectrum and X-ray analysis. 2·0.25Et2O·0.25MeOH crystallizes in the monoclinic system, space group C2/c with a = 20.117(4), b = 9.2705(19), c = 44.418(9) A^°, β= 93.19(3)°, V = 8271(3) A^°^3, Z = 8, Dc = 1.794 g/cm^3, T = 193 K, C31.25H43AuMo2NO0.50PS8, Mr = 1116.96, F(000) = 4380, μ(MoKa) = 4.603 mm^-1, S = 1.019, R = 0.0672 and wR = 0.1708 for 7243 observed reflections with I 〉 2σ(I). The anion of 2 consists of a butterfly-shaped Mo2S4Au core in which one [AuPPh3]^+ cation is coordinated by one bridging S and two terminal S atoms of the [(edt)2Mo2(S)2(μ-S)2] moiety. The Au(I) center adopts a pseudo-tetrahedral coordination geometry, and the Au-S bond lengths vary from 2.425(2) to 2.898(3)A^°.
In the presence of Et4NCl·H2O, reaction of AgCl with TabHPF6 in MeCN afforded the title complex {(Tab-Tab)[Ag2(μ-Cl)4]-2MeCN}n 1. 1 crystallizes in the orthorhombic space group Pbcn with a = 16.782(3), b = 6.8358(14), c = 26.194(5) A, V = 3004.9(10) A3, Z = 8,μ = 1.817 mm^-1, Dc = 1.711 g/cm3, T= 223 K, C1lH16AgCl2N2S, Mr= 387.10, F(000) = 1544, S= 1.160, R = 0.0528 and wR = 0.0896 for 2732 observed reflections with I 〉 2σ(I). 1 contains a 1D linear [Ag2Cl4]n^2n- chain coupled with the [Tab-Tab]2+ dications. Intermolecular hydrogen bonding interactions between the protons of methyl groups from the Tab-Tab dications and the chlorides result in the formation of a 2D hydrogen-bonded network.