Abstract
The Cs 2Re 6S 6Br 8 thiobromide, synthesized by high-temperature solid state route, has been used as precursor in order to prepare three new complex salts-( n-Bu 4N) 2Re 6S 6Br 8, Ca(DMSO) 6Re 6S 6Br 8 and Cs 2(18-crown-6) 3Re 6S 6Br 8-in which the [Re 6L 14] 2− anionic cluster unit is associated with a ramified cation ( n-Bu 4N) +, a solvated cation [Ca(DMSO) 6] 2+ and a 3:2 ‘club sandwich’ complex cation [Cs 2(18-crown-6) 3] 2+, respectively. The crystal structures, determined by single-crystal X-ray diffraction, evidence that the [(Re 6S i 6Br i 2)Br a 6] 2− octahedral cluster unit of the starting compound remains unchanged in the final compounds. The staking of the units as well as the inter-unit distances in these structures are discussed in relation to the size and the shape of the countercation. The distance between the cluster centers increases from 9.324 Å for the Cs 2Re 6S 6Br 8 precursor to 10.035, 10.722 and 11.995 Å for ( n-Bu 4N) 2Re 6S 6Br 8, Ca(DMSO) 6Re 6S 6Br 8 and Cs 2(18-crown-6) 3Re 6S 6Br 8, respectively.
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