Low temperature solid-state reactions of (NH4)2[MS4] (M = W, Mo) with [Cu(CH3CN)4](PF6) and CuBr in the presence of bis(diphenylphosphino)methane (dppm):: Crystal structures of [MS4Cu4(dppm)4](PF6)2 (M = W, Mo), [WS4Cu3(dppm)3]X (X = PF6,Br), [Cu3(dppm)3Br2]Br, [WS4Cu2(dppm)3], and [(n-Bu)4N][WS4Cu3Br2(dppm)2]

The solid-state reactions of(NH4)(2)[MS4] (M = W, Mo), [CU(CH3CN)(4)](PF6), and bis(diphenylphosphino)methane (dppm) at 110 degrees C produced pentanuclear clusters [MS4Cu4(dppm)(4)](PF6)2 (1, M = W; 2, M = Mo), while the analogous solution reaction in CH2Cl2 for M = W yielded a tetranuclear cluster [WS4Cu3(dppm)(3)] (P-F) (3). On the other hand. the (NH4)(2)[WS4]/CuBr/dppm reaction system resulted in the formation of a tetranuclear cluster [WS4Cu3(dppm)(3)]Br (4) either in solid at 110 degrees C or in CH2Cl2, where the solid-state reaction gave also [Cu-3(dppm)(3)-Br-2]Br (5) as a side product. When the solid-state reactions between (NH4)(2)[WS4], [Cu(CH3CN)(4)](PF6) (or CuBr), and dppm were carried out under the presence of [(n-Bu)(4)N]Br, [WS4Cu2(dppm)(3)] (6) and [(n-Bu)(4)N][WS4Cu3-Br-2(dppm)(2)] (7) were generated, respectively, while the corresponding solution reactions in CH2Cl2 gave rise to 3 and 4. Compounds 1-7 were fully characterized. 1 crystallizes in the orthorhombic space group Pnma with a = 37.871(6) Angstrom, b = 19.667(4) Angstrom, c 14.836(4) Angstrom, and Z = 4. 2 crystallizes in the orthorhombic space group Pnma with a = 38.00(3) Angstrom, b = 19.65(1) Angstrom, c = 14.80(1) Angstrom, and Z = 4. 3 . CH2Cl2 crystallizes in the monoclinic space group P2(1) with a 13.185(5) Angstrom, b = 17.234(6) Angstrom, c = 17.791(2) Angstrom beta = 90.83(4)degrees, and Z = 2. 4 . CH2Cl2 crystallizes in the monoclinic space group P2(1) with a = 12.94(2) Angstrom, beta = 17.06(1) Angstrom, c = 17.875(7) Angstrom, b = 93.7(1)degrees, and Z = 2. 5 2(CH3)(2)CHOH crystallizes in the triclinic space group P (1) over bar with a = 15.613(5) Angstrom, beta = 18.440(6) Angstrom, c = 14.191(8) Angstrom, alpha = 99.86(4)degrees, beta = 104.14(4)degrees, gamma 86.79(3)degrees, and Z = 2. 6 . CH2Cl2 crystallizes in the triclinic space group P (1) over bar with alpha = 14.60(3) Angstrom, b = 25.6(1) Angstrom, c 10.98(1) Angstrom, alpha = 92.9(3)degrees, beta = 105.1(1)degrees, gamma = 78.7(4)degrees, and Z = 2. 7 . 1.5CH(2)Cl(2) crystallizes in the monoclinic space group P2(1)/n with a = 10.842(3) Angstrom, b = 31.08(2) Angstrom, c = 22.713(5) Angstrom, beta = 101.29(2)degrees, and Z = 4.