THE CRYSTAL AND MOLECULAR STRUCTURE OF A SERIES OF OXO MOLYBDENUM DITHIOCARBAMATES

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Abstract
The crystal and molecular structure of a series of oxo-molybdenun di-n-propyldithiocarbamates have been studied by X-ray diffraction methods. The compounds studied were di(oxo-di-n-propyldithiocarbamato) molybdenum VI (A), μ-oxo-bis-(di(oxo-di-n-propyldithiocarbamato) molybdenum V) (B), and oxo-bis-di-n-propyldithiocarbamato molybdenum IV (C). Compound A is orthorhombic, space group Pbca, with eight molecules in a unit cell having dimensions a =16.577(3) Å, b =18.771(3) Å and c =13.702(2) Å. The molybdenum V compound (B) crystallizes in the orthorhombic non-centrosymmetric space group Pca21, with four molecules in a unit cell having parameters a =19.605(6) Å, b =13.491(3) Å and c =16.342(4) Å. The last compound (C) is triclinic, space group P1 with two molecules in the unit cell. Its crystal parameters are a =10.183(6) Å, b =13.012(9) Å, c =9.208(5) Å' a =71.57(5)°, β =105.81(5)° and γ =81.82(5)°. The intensities were collected by counter techniques using MoKa radiation. All structures were refined by full matrix least-squares, using anisotropic temperature factors for all non-hydrogen atoms. For each compound, respectively, these refinements were conducted on 2795, 3216 and 2346 reflections and the corresponding R factors were 0.052, 0.052 and 0.063. The dioxo molybdenum VI compound contains two oxygen atoms in cis position, as it is usually observed in these compounds. The four sulfur atoms occupy the remaining four positions of an octahedron around molybdenum. This octahedron is deformed by steric interactions between the sulfur atoms. The molybdenum V complex possesses a similar geometry around each molybdenum. A common oxygen atom bridges the two metal atoms. This structure is similar to that of Mo2O3(S2COC2H5)4. The ligand around the molybdenum IV complex form a square pyramid. The four sulfur atoms occupy the basal plane and the oxygen is at the summit of the pyramid.