Dithiolate clusters of copper(i): utilization of all possible coordination sites of 1-(diethoxyphosphinyl)-1-cyanoethylene-2,2-dithiolate

Four CuI–S clusters, 1–4, containing bridging dppm and 2-(diethoxyphosphinyl)-2-cyanoethylene-1,1-dithiolato ligands were isolated from the reaction of [Cu2(μ-dppm)2(CH3CN)2](PF6)2 and K2S2CC(CN)P(O)(OEt)2 in CH2Cl2. The cluster nuclearity depends on the coordination pattern of the functionalized 1,1-dithiolates: 1 and 2, Cu4(dppm)4[S2CC(CN)P(O)(OEt)2]2 and Cu4(dppm)3(OPPh2CH2PPh2)[S2CC(CN)P(O)(OEt)2]2, display a tetrametallic tetraconnective (μ-S, μ-S) bridging mode; in 3, Cu5(dppm)4[S2CC(CN)P(O)(OEt)2]2(PF6), exhibits a novel tetrametallic pentaconnective coordination pattern; in 4, Cu9(dppm)4[S2CC(CN)P(O)(OEt)2]4(PF6), reveals an unprecedented pentametallic hexaconnective coordination pattern. Pertinent crystallographic data are: 1, C114H108Cu4N2O6P10S4·CH2Cl2, monoclinic, P21/n, a = 20.1464(11), b = 23.4222(13), c = 23.7695(14) Å, β = 91.837(1)°, V = 11210(1) Å3, Z = 4; 2, C114H108Cu4N2O7P10S4, monoclinic, P21/n, a = 15.6463(8), b = 52.324(3), c = 15.8286(8) Å, β = 118.529(1)°, V = 11385(1) Å3, Z = 4; 3, C114H116Cu5F6N2O10P11S4, monoclinic, C2/c, a = 20.4306(11), b = 22.6378(12), c = 26.1927(13) Å, β = 90.886(1)°, V = 12112.8(11) Å3, Z = 4; 4, C128H128Cu9F6N4O12P13S8, orthorhombic, Pna21, a = 38.8644(11), b = 24.3585(8), c = 16.0870(5) Å, V = 15229.2(8) Å3, Z = 4.