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The yellow-transparent, air stable solid GeGa 4 S 4  ( a  = 1142.50(9) pm,  Z  = 8,  Pa [unk]) is a new isotypic member of the family of cubic MM′ 4 X 4  compounds (M: Sn, Ge, M′: Ga, In, X: S, Se) with S atoms in a  ψ -tetrahedral coordination (one lone pair, three gallium atoms). Striking feature of the structure is a slightly distorted tetrahedral cationic cluster [GeGa 4 ] 8+  with hitherto unknown covalent Ge–Ga bonds ( d  Ge-Ga  ≈ 244 pm). Ga is tetrahedrally coordinated by one Ge and three S atoms with the Ge atom common to four GaGeS 3  tetrahedra resulting in the formation of GeGa 4 S 12  groups (truncated tetrahedra). Detailed analyses of the geometrical conditions of the crystal structure in connection with systematic X-ray studies of selected mixed crystal systems show an anomalous short non-bonding S–S contact to be responsible for the low flexibility of the structure with respect to substitution of M, M′ and X by other elements. In particular the non-existence of tellurides of this structure type can be made reasonable.

The new heteronuclear cluster cation [GeGa 4 ] 8+ in GeGa 4 S 4 : a summary of single crystal and mixed crystal studies