First Examples of Chalcofluoride Rhenium Cluster Complexes with Cubane‐Like Anions [Re 4 Q 4 F 12 ] 4– (Q = S, Se)

Two rhenium tetrahedral cluster chalcofluoride compounds, K 4 [Re 4 S 4 F 12 ] · 3.4 H 2 O ( 1 ) and K 4 [Re 4 Se 4 F 12 ] · 6 H 2 O ( 2 ), have been synthesized for the first time by a reaction of Re 4 Q 4 (TeCl 2 ) 4 Cl 8 (Q = S, Se) with molten KHF 2 . Both compounds have been characterized by single‐crystal X‐ray diffraction methods. Compound 1 crystallizes in the trigonal space group R $\tilde {3}$ with 24 formula units per cell [ a = b = 23.6503(3) Å, c = 25.2697(7) Å, V = 12240.6(4) Å 3 ( T = 293 K)]; compound 2 crystallizes in the monoclinic space group P $\tilde {1}$ with four formula units per cell [ a = 10.6451(3) Å, b = 14.6853(4) Å, c = 16.9349(5) Å, α = 66.8420(10)°, β = 84.8460(10)°, γ = 85.5740(10)°, V = 2421.69(12) Å 3 ( T = 293 K)]. Hydrophilic terminal fluoride ligands of cluster anions are included in the hydrogen bond systems of their hydrate shells. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)