Octahedral Hexahydroxo Rhenium Cluster Complexes [Re₆Q₈(OH)₆]^4–·(Q = S, Se): Synthesis, Structure, and Properties

Abstract

Abstract Two novel rhenium cluster compounds, K 4 [Re 6 S 8 (OH) 6 ] · 8H 2 O ( 1 ) and K 4 [Re 6 Se 8 (OH) 6 ] · 8H 2 O ( 2 ), containing octahedral cluster chalcogenide anionic complexes [Re 6 Q 8 (OH) 6 ] 4– with terminal hydroxo ligands have been synthesized by the reaction of Re 6 Q 8 Br 2 (Q = S, Se) with molten KOH. Two chalcohalide compounds, one known (Cs 4 [Re 6 S 8 Br 6 ] · 2H 2 O, 3 ) and another new (Cs 3 [Re 6 Se 8 Cl 6 ] · 2H 2 O, 4 ), were prepared by reactions of 1 and 2 with CsX and HX (X = Br, Cl) in an aqueous solution. Compounds 1 , 2 , and 4 have been characterized by the single‐crystal X‐ray diffraction method. Compounds 1 and 2 are crystallized in triclinic space group P $\bar {1}$ with one formula unit in the cell of dimensions a = 8.4936(8) Å, b = 8.9101(11) Å, c = 10.5940(13) Å, α = 77.935(11)°, β = 75.933(9)°, γ = 71.244(10)°, V = 728.9(1) Å 3 (compound 1 ) and a = 8.613(1) Å, b = 8.996(1) Å, c = 10.057(1) Å, α = 78.587(2)°, β = 77.811(2)°, γ = 71.728(2)°, V = 715.9(2) Å 3 (compound 2 ). Compound 4 crystallizes in the monoclinic space group P 2 1 / n with two formula units in the cell of dimensions a = 9.819(3) Å, b = 12.925(4) Å, c = 11.756(4) Å, β = 113.38(3)°, V = 1369.6(8) Å 3 . Compounds 1 and 2 display luminescent properties. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)