The DMSO Solvated octahedro ‐[W 6 Cl i 12 ]Cl 6 a Cluster Molecule

Octahedro ‐hexatungsten octadecachloride, W 6 Cl 18 , is soluble in dimethyl sulfoxide (DMSO). Brownish black crystals of W 6 Cl 18 (DMSO) 4 are formed from the brown solution by evaporation of DMSO under dynamic vacuum. The compound crystallizes monoclinically in the space group  P 2 1 / n (no. 14) with a  = 10.420 Å, b  = 9.271 Å, c  = 20.828 Å, β = 91.10° and Z  = 2. The crystal structure is formed by isolated cluster molecules [W 6 Cl   i 12 ]Cl   6 aof the hexameric tungsten trichloride and DMSO molecules. It is the first hierarchical variant of the tetragonal BaAl 4 type of structure where all atoms of the intermetallic phase are substituted by neutral molecules. The mean bond lengths are d(W–W) = 2.878 Å, d(W–Cl i ) = 2.391 Å and d(W–Cl a ) = 2.447 Å. They will be discussed in relation to analogous clusters. The two crystallographically independent DMSO molecules (d(S–O) = 1.53–1.55 Å, d(S–C) = 1.65–1.78 Å) form a 3 D net of condensed < 4 8 6 4  > dodecahedra which envelopes the clusters.