Research Article: Octa­kis(dimethyl sulfoxide-κO)cerium(III) μ6-oxido-dodeca-μ2-oxido-hexa­oxidohexa­molybdate(VI) dimethyl sulfoxide tetrasolvate

Date Published: July 01, 2012

Publisher: International Union of Crystallography

Author(s): Arbia Ben Khélifa, Michel Giorgi, Mohamed Salah Belkhiria.


The title complex, [Ce(C2H6OS)8]2[Mo6O19]3·4C2H6OS, was obtained as a byproduct of the reaction of [(C4H9)4N]2[Mo6O19] with Ce(NO3)3·6H2O and phthalic acid in dimethyl­sulfoxide solution. The asymmetric unit consists of a complex [Ce(C2H6OS)8]3+ cation, one and a half of the Lindqvist-type [Mo6O19]2− polyanions and two dimethyl­sulfoxide solvent mol­ecules; the half polyanion lies on an inversion center. The Ce3+ ion is coordinated by eight dimethyl­sulfoxide ligands through the O atoms in the form of a distorted square antiprism. The Ce—O bond lengths range from 2.429 (6) to 2.550 (5) Å. The cohesion of the structure is ensured by S⋯O [3.115 (6), 3.242 (10) and 3.12 (3) Å], O⋯O [3.037 (10) Å] and C—H⋯O inter­actions between cations and anions. The S and C atoms of a dmso ligand are disordered over three sites in a 0.45:0.30:0.25 ratio. The dimethyl­sulfoxide solvent mol­ecules are highly disordered and could not be modelled successfully; their contribution was therefore removed from the refinement using the SQUEEZE routine in PLATON [Spek (2009 ▶). Acta Cryst. D65, 148–155]. Potential solvent-accessible voids of 500.0 Å3 occur in the crystal structure.

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For general background, physical properties and applications of polyoxidometalates, see: Dolbecq et al. (2010 ▶). For the synthesis of [(C4H9)4N]2[Mo6O19], see: Hur et al. (1990 ▶). For related structures, see: Wang et al. (2003 ▶); Koo & Lee (2006 ▶); Qiu et al. (2006 ▶). For crystallographic analysis, see: Spek (2009 ▶).




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