SOLID-STATE SYNTHESIS OF COPPER(I) THIOTUNGSTATE CLUSTER COMPOUNDS AT LOW HEATING TEMPERATURES - CRYSTAL-STRUCTURES OF [(N-BU)(4)N](3)-[WS4CU3CL3BR] AND [ET(4)N](4)[WS4CU4I6]

Reaction of [NH4](2)[WS4] with CuX (X = Cl or I) and R(4)NX (R = Et or n-Bu) in the solid state gave two new bimetallic compounds with W:Cu compositions from 1:3 to 1:4. Compound (1), [(n-Bu)(4)N](3)[WS4Cu3Cl3Br], crystallizes in the hexagonal space group R3c with a = 17.051(5), c = 38.372(5) Angstrom, V = 9661.8 Angstrom(3), Z = 6. The cluster anion of (1) comprises a cubane-like cluster core [WS3Cu3Br] of C-3 symmetry with a Cl atom attached to each of the three Cu atoms and one terminal sulphido ligand attached to the W atom. Compound (2), [Et(4)N](4)[WS4Cu4I6], crystallizes in the monoclinic space group C2/m with a=29.702(6), b=12.7887(5), c= 15.327(3)Angstrom, beta=99.69(2)degrees, V=5738.1 Angstrom(3) Z=4. In the cluster anion of (2), four edges of the WS4 core are coordinated by four Cu atoms, giving a WS4Cu4 aggregate of approximate C-2v symmetry.