Synthesis, properties, and crystal and molecular structures of the complexes [Mo(XC6H4CSN2)(XC6H 4CSN2H)(XC6H4CSNNC(CH 3)2)] (X = p-Cl, p-Me). Species possessing three chemically and crystallographically distinct chelate rings

Jonathan R. Dilworth, Phillip L. Dahlstrom, Jeffrey R. Hyde, Maryanne Kustyn, Philip A. Vella, Jon A Zubieta

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The crystal and molecular structures of the complexes [Mo(XC6H4CSN2)(XC6H 4CSN2H)(XC6H4CSNNCMe2)], X = CH3 (III) and Cl (IV), have been investigated by X-ray diffraction techniques. Compound III crystallizes in the triclinic space group P1 with two molecules in the unit cell of dimensions a = 12.505 (9) Å, b = 12.533 (10) Å, c = 10.274 (8) Å, α = 115.62 (1)°, β = 86.41 (2)°, and γ = 93.45 (1)°, while compound IV displays monoclinic symmetry, space group P21/c with four molecules in the unit cell of dimensions a = 13.049 (1) Å, b = 12.838 (1) Å, c = 17.183 (1) Å, and β = 90.87 (1)°. The structures were solved by using 2573 and 2889 symmetry-independent reflections, respectively, with I ≥ 2.58σ(I). Refinement by full-matrix least-squares methods, using anisotropic temperature factors for all nonhydrogen atoms, gave a final R factor of 0.073 for III. Similar refinement, with the inclusion of hydrogen atoms with isotropic thermal parameters, yielded a final residual of 0.038 for IV. The structures are essentially identical with a coordination polyhedra intermediate between trigonal-prismatic and octahedral geometries with the sulfur and nitrogen donor atoms disposed on opposite triangular faces in a facial configuration. In complex IV the chelate rings exhibit Mo-N bond distances and Mo-N-N valence angles of 1.786 (5) Å and 142.8 (3)° for the diazenido(1-) ligand, 1.967 (5) Å and 131.6 (4)° for the diazene ring, and 2.216 (5) Å and 116.9 (4)° for the hydrazonido form. The Mo-S distance of 2.48 Å for the sulfur trans to the multiply bonded diazenido nitrogen is significantly longer than the average distance 2.457 (2) Å for the other Mo-S bonds and indicates a structural trans influence. The severe distortions from the trigonal-prismatic geometry are partially steric in origin, arising from the introduction of the hydrazonido group and resultant nonbonding interactions in the N1N3N5 plane.

Original languageEnglish (US)
Pages (from-to)3562-3572
Number of pages11
JournalInorganic Chemistry
Issue number12
StatePublished - 1980
Externally publishedYes


ASJC Scopus subject areas

  • Inorganic Chemistry

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