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Journal of Structural Chemistry

2011 year, number 1

CRYSTAL STRUCTURES OF (H7O3)2[(Mo6Cl7.22I0.78)Cl6]·3H2O, (H9O4)2[(Mo6Cl6.66I1.34)Cl6] AND (H5O2)2[(Mo6Cl6.36I1.64)Cl6]·2H2O: DRASTIC CHANGES IN PACKING CAUSED BY SMAL VARIATIONS IN THE CHEMICAL COMPOSITIONS OF THE CLUSTER CORES

M. N. Sokolov1, М. А. Mikhailov2, А. V. Virovets3, V. P. Fedin4
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Keywords: molybdenum, iodine, chlorine, clusters, X-ray structure, packing topology, mass-spectra
Pages: 170-175

Abstract

The crystal structures of three new chloride-iodide cluster complexes of Mo(II) of the compositions (H7O3)2[(Mo6Cl7.22I0.78)Cl6]·3H2O (1), (H9O4)2[(Mo6Cl6.66I1.34)Cl6] (2), and (H5O2)2[(Mo6Cl6.36I1.64)Cl6]·2H2O (3) are determined. All cluster anions in 1-3 are derived from octahedral halide-bridged clusters {Mo63-Hal)8}4+ (Hal = Cl, I). The iodide ligands are disordered over three μ3-positions. According to mass-spectrometry, all these compounds are solid solutions of the hydroxonium salts of [(Mo6Cl6I2)Cl6]2- and [(Mo6Cl7I)Cl6]2-. Small changes in the iodine content of the cluster cores give rise to changes in the composition of the hydroxonium cations, in the hydrogen bonding network and can lead to changes in the structural type. The cluster anions are packed according to the fcc (1, 3) or hcp (2) motifs.