Preparation and crystal and molecular structure of a tris(thiobenzoyldiazene)molybdenum complex: An example of distorted trigonal-prismatic coordination

Jonathan R. Dilworth, J. Hyde, P. Lyford, P. Vella, K. Venkatasubramaman, Jon A Zubieta

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Abstract

Molybdenum dioxobis(acetylacetonate), [MoO2(acac)2], or sodium molybdate reacts with the thioaroylhydrazines RNHNHCSR′ (R = H, R′ = C6H5, p-MeC6H4, p-MeOC6H4; R = Ph, R′ = PhCH2, 1-C10H7, p-MeC6H4, p-MeOC6H4) to give the dark green or black complexes [Mo(RN2CSR′)3]. The structure of tris(thiobenzoyldiazene)molybdenum-(VI)-dimethylformamide, [Mo(C6H5CSN2H)3]·(CH 3)2NCHO, has been determined in a single-crystal X-ray diffraction study. The coordination geometry of the molybdenum is a distorted trigonal prism of sulfur and nitrogen donor atoms contributed by three chelating diazene ligands disposed in a facial configuration. The distortion may be expressed in terms of an average twist angle of 7°, compared to the value of α = 0° for a regular trigonal prism. The average molybdenum-sulfur bond distance is 2.400 (5) Å and the average molybdenum-nitrogen bond distance is 2.03 (1) Å. The bond lengths in the chelate ring systems Mo-N-N-C-S- are intermediate between single- and double-bond distances, suggesting considerable delocalization of charge: N-N(av) = 1.32 (2), N-C(av) = 1.35 (2) Å, C-S(av) = 1.69 (2) Å. The complex crystallizes in the orthorhombic system, space group Pbca, with a = 17.458 (8) Å, b = 17.541 (9) Å, and c = 17.896 (9) Å. The measured density of 1.51 ± 0.03 g/cm3 requires eight molecules per unit cell (ρcalcd = 1.50 g/cm3). The structure was solved by conventional Patterson and Fourier synthesis methods from 1456 independent reflections with I > 2.58σ(I). Full-matrix least-squares refinement of all atoms, excluding hydrogens, converged at values for R1 = 0.071 and R2 = 0.077.

Original languageEnglish (US)
Pages (from-to)268-274
Number of pages7
JournalInorganic Chemistry
Volume18
Issue number2
StatePublished - 1979
Externally publishedYes

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Molybdenum
Molecular structure
molybdenum
molecular structure
Crystal structure
preparation
crystal structure
Prisms
Sulfur
prisms
Nitrogen
sulfur
nitrogen
Dimethylformamide
Atoms
molybdates
Bond length
Chelation
chelates
Hydrogen

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

Preparation and crystal and molecular structure of a tris(thiobenzoyldiazene)molybdenum complex : An example of distorted trigonal-prismatic coordination. / Dilworth, Jonathan R.; Hyde, J.; Lyford, P.; Vella, P.; Venkatasubramaman, K.; Zubieta, Jon A.

In: Inorganic Chemistry, Vol. 18, No. 2, 1979, p. 268-274.

Research output: Contribution to journalArticle

Dilworth, Jonathan R. ; Hyde, J. ; Lyford, P. ; Vella, P. ; Venkatasubramaman, K. ; Zubieta, Jon A. / Preparation and crystal and molecular structure of a tris(thiobenzoyldiazene)molybdenum complex : An example of distorted trigonal-prismatic coordination. In: Inorganic Chemistry. 1979 ; Vol. 18, No. 2. pp. 268-274.
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title = "Preparation and crystal and molecular structure of a tris(thiobenzoyldiazene)molybdenum complex: An example of distorted trigonal-prismatic coordination",
abstract = "Molybdenum dioxobis(acetylacetonate), [MoO2(acac)2], or sodium molybdate reacts with the thioaroylhydrazines RNHNHCSR′ (R = H, R′ = C6H5, p-MeC6H4, p-MeOC6H4; R = Ph, R′ = PhCH2, 1-C10H7, p-MeC6H4, p-MeOC6H4) to give the dark green or black complexes [Mo(RN2CSR′)3]. The structure of tris(thiobenzoyldiazene)molybdenum-(VI)-dimethylformamide, [Mo(C6H5CSN2H)3]·(CH 3)2NCHO, has been determined in a single-crystal X-ray diffraction study. The coordination geometry of the molybdenum is a distorted trigonal prism of sulfur and nitrogen donor atoms contributed by three chelating diazene ligands disposed in a facial configuration. The distortion may be expressed in terms of an average twist angle of 7°, compared to the value of α = 0° for a regular trigonal prism. The average molybdenum-sulfur bond distance is 2.400 (5) {\AA} and the average molybdenum-nitrogen bond distance is 2.03 (1) {\AA}. The bond lengths in the chelate ring systems Mo-N-N-C-S- are intermediate between single- and double-bond distances, suggesting considerable delocalization of charge: N-N(av) = 1.32 (2), N-C(av) = 1.35 (2) {\AA}, C-S(av) = 1.69 (2) {\AA}. The complex crystallizes in the orthorhombic system, space group Pbca, with a = 17.458 (8) {\AA}, b = 17.541 (9) {\AA}, and c = 17.896 (9) {\AA}. The measured density of 1.51 ± 0.03 g/cm3 requires eight molecules per unit cell (ρcalcd = 1.50 g/cm3). The structure was solved by conventional Patterson and Fourier synthesis methods from 1456 independent reflections with I > 2.58σ(I). Full-matrix least-squares refinement of all atoms, excluding hydrogens, converged at values for R1 = 0.071 and R2 = 0.077.",
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T1 - Preparation and crystal and molecular structure of a tris(thiobenzoyldiazene)molybdenum complex

T2 - An example of distorted trigonal-prismatic coordination

AU - Dilworth, Jonathan R.

AU - Hyde, J.

AU - Lyford, P.

AU - Vella, P.

AU - Venkatasubramaman, K.

AU - Zubieta, Jon A

PY - 1979

Y1 - 1979

N2 - Molybdenum dioxobis(acetylacetonate), [MoO2(acac)2], or sodium molybdate reacts with the thioaroylhydrazines RNHNHCSR′ (R = H, R′ = C6H5, p-MeC6H4, p-MeOC6H4; R = Ph, R′ = PhCH2, 1-C10H7, p-MeC6H4, p-MeOC6H4) to give the dark green or black complexes [Mo(RN2CSR′)3]. The structure of tris(thiobenzoyldiazene)molybdenum-(VI)-dimethylformamide, [Mo(C6H5CSN2H)3]·(CH 3)2NCHO, has been determined in a single-crystal X-ray diffraction study. The coordination geometry of the molybdenum is a distorted trigonal prism of sulfur and nitrogen donor atoms contributed by three chelating diazene ligands disposed in a facial configuration. The distortion may be expressed in terms of an average twist angle of 7°, compared to the value of α = 0° for a regular trigonal prism. The average molybdenum-sulfur bond distance is 2.400 (5) Å and the average molybdenum-nitrogen bond distance is 2.03 (1) Å. The bond lengths in the chelate ring systems Mo-N-N-C-S- are intermediate between single- and double-bond distances, suggesting considerable delocalization of charge: N-N(av) = 1.32 (2), N-C(av) = 1.35 (2) Å, C-S(av) = 1.69 (2) Å. The complex crystallizes in the orthorhombic system, space group Pbca, with a = 17.458 (8) Å, b = 17.541 (9) Å, and c = 17.896 (9) Å. The measured density of 1.51 ± 0.03 g/cm3 requires eight molecules per unit cell (ρcalcd = 1.50 g/cm3). The structure was solved by conventional Patterson and Fourier synthesis methods from 1456 independent reflections with I > 2.58σ(I). Full-matrix least-squares refinement of all atoms, excluding hydrogens, converged at values for R1 = 0.071 and R2 = 0.077.

AB - Molybdenum dioxobis(acetylacetonate), [MoO2(acac)2], or sodium molybdate reacts with the thioaroylhydrazines RNHNHCSR′ (R = H, R′ = C6H5, p-MeC6H4, p-MeOC6H4; R = Ph, R′ = PhCH2, 1-C10H7, p-MeC6H4, p-MeOC6H4) to give the dark green or black complexes [Mo(RN2CSR′)3]. The structure of tris(thiobenzoyldiazene)molybdenum-(VI)-dimethylformamide, [Mo(C6H5CSN2H)3]·(CH 3)2NCHO, has been determined in a single-crystal X-ray diffraction study. The coordination geometry of the molybdenum is a distorted trigonal prism of sulfur and nitrogen donor atoms contributed by three chelating diazene ligands disposed in a facial configuration. The distortion may be expressed in terms of an average twist angle of 7°, compared to the value of α = 0° for a regular trigonal prism. The average molybdenum-sulfur bond distance is 2.400 (5) Å and the average molybdenum-nitrogen bond distance is 2.03 (1) Å. The bond lengths in the chelate ring systems Mo-N-N-C-S- are intermediate between single- and double-bond distances, suggesting considerable delocalization of charge: N-N(av) = 1.32 (2), N-C(av) = 1.35 (2) Å, C-S(av) = 1.69 (2) Å. The complex crystallizes in the orthorhombic system, space group Pbca, with a = 17.458 (8) Å, b = 17.541 (9) Å, and c = 17.896 (9) Å. The measured density of 1.51 ± 0.03 g/cm3 requires eight molecules per unit cell (ρcalcd = 1.50 g/cm3). The structure was solved by conventional Patterson and Fourier synthesis methods from 1456 independent reflections with I > 2.58σ(I). Full-matrix least-squares refinement of all atoms, excluding hydrogens, converged at values for R1 = 0.071 and R2 = 0.077.

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