Synthesis and chemical characterization of diazenido derivatives of oxomolybdate clusters: The structures of the tetranuclear complexes [Mo4O8)(OR)2(NNC6H5]2- (R = CH3 OR C2H5)

T. C. Hsieh, Jon A Zubieta

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Abstract

α-[Mo8O26 4- reacts with phenylhydrazine in alcohols to yield tetranuclear clusters of the type [Mo4O8(OR)2(NNC6H5)4]2-, with R = CH3, C2H5 or CH(CH3)2, depending on the solvent alcohol employed. The crystallizations from alcohol-ether mixtures afford single crystals of the various derivaives. (HNEt3)2[Mo4O8(OCH3)2(NNC6H5)4] (1) crystallizes in the triclinic space group P1, a = 12.326(3) Å, b = 12.799(3) Å, c = 16.190(3) Å, α = 83.56(1)°, β = 83.94(1)°, γ = 83.67(1)°, V = 2521(1) Å3, Z = 2. Refinement based on 4243 reflections converged at a residual of 0.050. One form of {A figure is presented} (1a) crystallizes in the monoclinic space group PP1/c, a = 19.735(4) Å, b = 16.222(3) Å, c = 23.802(4) Å, β = 111.92(1)°, V = 7069(2) Å3, Z = 4. Refinement was based on 3390 reflections and converged at a residual of 0.050. One form of {A figure is presented} (2) is isomorphous with 1a, crystallizing in the monoclinic space group P21/c, a = 19.840(3) Å, b = 16.445(3) Å, c = 24.074(4) Å, β = 112.39(1)°, V = 7264(1) Å3, Z = 4; refinement converged at a value of 0.060 for the conventional R factor. A second modification of (NBun 4)2[Mo4O8(OC2H5)2(NNC6H5)4] crystallizes in the tetragonal space group I41/a, a = 35.236(6) Å, b = 35.236(6) Å, c = 12.137(4) Å, V = 15066.0(13) Å3, Z = 8. Refinement based on 1734 reflections converged at a residual of 0.082. The structures consist of discrete tetranuclear units, presenting cis-bisdiazenido moieties, [Mo(NNC6H5)2]2+, bridged by two alkoxy groups and two tetra-oxomolybdate, [MoO4]2-, fragments.

Original languageEnglish (US)
Pages (from-to)305-314
Number of pages10
JournalPolyhedron
Volume5
Issue number1-2
DOIs
StatePublished - 1986
Externally publishedYes

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Alcohols
Derivatives
synthesis
alcohols
R Factors
Crystallization
Ether
Ethers
Single crystals
ethers
fragments
methylidyne
crystallization
single crystals
phenylhydrazine
alkoxyl radical
molybdate

ASJC Scopus subject areas

  • Biochemistry
  • Inorganic Chemistry
  • Physical and Theoretical Chemistry
  • Materials Chemistry

Cite this

@article{9f7bf65cda1448a79965b39bc6b9a157,
title = "Synthesis and chemical characterization of diazenido derivatives of oxomolybdate clusters: The structures of the tetranuclear complexes [Mo4O8)(OR)2(NNC6H5]2- (R = CH3 OR C2H5)",
abstract = "α-[Mo8O26 4- reacts with phenylhydrazine in alcohols to yield tetranuclear clusters of the type [Mo4O8(OR)2(NNC6H5)4]2-, with R = CH3, C2H5 or CH(CH3)2, depending on the solvent alcohol employed. The crystallizations from alcohol-ether mixtures afford single crystals of the various derivaives. (HNEt3)2[Mo4O8(OCH3)2(NNC6H5)4] (1) crystallizes in the triclinic space group P1, a = 12.326(3) {\AA}, b = 12.799(3) {\AA}, c = 16.190(3) {\AA}, α = 83.56(1)°, β = 83.94(1)°, γ = 83.67(1)°, V = 2521(1) {\AA}3, Z = 2. Refinement based on 4243 reflections converged at a residual of 0.050. One form of {A figure is presented} (1a) crystallizes in the monoclinic space group PP1/c, a = 19.735(4) {\AA}, b = 16.222(3) {\AA}, c = 23.802(4) {\AA}, β = 111.92(1)°, V = 7069(2) {\AA}3, Z = 4. Refinement was based on 3390 reflections and converged at a residual of 0.050. One form of {A figure is presented} (2) is isomorphous with 1a, crystallizing in the monoclinic space group P21/c, a = 19.840(3) {\AA}, b = 16.445(3) {\AA}, c = 24.074(4) {\AA}, β = 112.39(1)°, V = 7264(1) {\AA}3, Z = 4; refinement converged at a value of 0.060 for the conventional R factor. A second modification of (NBun 4)2[Mo4O8(OC2H5)2(NNC6H5)4] crystallizes in the tetragonal space group I41/a, a = 35.236(6) {\AA}, b = 35.236(6) {\AA}, c = 12.137(4) {\AA}, V = 15066.0(13) {\AA}3, Z = 8. Refinement based on 1734 reflections converged at a residual of 0.082. The structures consist of discrete tetranuclear units, presenting cis-bisdiazenido moieties, [Mo(NNC6H5)2]2+, bridged by two alkoxy groups and two tetra-oxomolybdate, [MoO4]2-, fragments.",
author = "Hsieh, {T. C.} and Zubieta, {Jon A}",
year = "1986",
doi = "10.1016/S0277-5387(00)84927-X",
language = "English (US)",
volume = "5",
pages = "305--314",
journal = "Polyhedron",
issn = "0277-5387",
publisher = "Elsevier",
number = "1-2",

}

TY - JOUR

T1 - Synthesis and chemical characterization of diazenido derivatives of oxomolybdate clusters

T2 - The structures of the tetranuclear complexes [Mo4O8)(OR)2(NNC6H5]2- (R = CH3 OR C2H5)

AU - Hsieh, T. C.

AU - Zubieta, Jon A

PY - 1986

Y1 - 1986

N2 - α-[Mo8O26 4- reacts with phenylhydrazine in alcohols to yield tetranuclear clusters of the type [Mo4O8(OR)2(NNC6H5)4]2-, with R = CH3, C2H5 or CH(CH3)2, depending on the solvent alcohol employed. The crystallizations from alcohol-ether mixtures afford single crystals of the various derivaives. (HNEt3)2[Mo4O8(OCH3)2(NNC6H5)4] (1) crystallizes in the triclinic space group P1, a = 12.326(3) Å, b = 12.799(3) Å, c = 16.190(3) Å, α = 83.56(1)°, β = 83.94(1)°, γ = 83.67(1)°, V = 2521(1) Å3, Z = 2. Refinement based on 4243 reflections converged at a residual of 0.050. One form of {A figure is presented} (1a) crystallizes in the monoclinic space group PP1/c, a = 19.735(4) Å, b = 16.222(3) Å, c = 23.802(4) Å, β = 111.92(1)°, V = 7069(2) Å3, Z = 4. Refinement was based on 3390 reflections and converged at a residual of 0.050. One form of {A figure is presented} (2) is isomorphous with 1a, crystallizing in the monoclinic space group P21/c, a = 19.840(3) Å, b = 16.445(3) Å, c = 24.074(4) Å, β = 112.39(1)°, V = 7264(1) Å3, Z = 4; refinement converged at a value of 0.060 for the conventional R factor. A second modification of (NBun 4)2[Mo4O8(OC2H5)2(NNC6H5)4] crystallizes in the tetragonal space group I41/a, a = 35.236(6) Å, b = 35.236(6) Å, c = 12.137(4) Å, V = 15066.0(13) Å3, Z = 8. Refinement based on 1734 reflections converged at a residual of 0.082. The structures consist of discrete tetranuclear units, presenting cis-bisdiazenido moieties, [Mo(NNC6H5)2]2+, bridged by two alkoxy groups and two tetra-oxomolybdate, [MoO4]2-, fragments.

AB - α-[Mo8O26 4- reacts with phenylhydrazine in alcohols to yield tetranuclear clusters of the type [Mo4O8(OR)2(NNC6H5)4]2-, with R = CH3, C2H5 or CH(CH3)2, depending on the solvent alcohol employed. The crystallizations from alcohol-ether mixtures afford single crystals of the various derivaives. (HNEt3)2[Mo4O8(OCH3)2(NNC6H5)4] (1) crystallizes in the triclinic space group P1, a = 12.326(3) Å, b = 12.799(3) Å, c = 16.190(3) Å, α = 83.56(1)°, β = 83.94(1)°, γ = 83.67(1)°, V = 2521(1) Å3, Z = 2. Refinement based on 4243 reflections converged at a residual of 0.050. One form of {A figure is presented} (1a) crystallizes in the monoclinic space group PP1/c, a = 19.735(4) Å, b = 16.222(3) Å, c = 23.802(4) Å, β = 111.92(1)°, V = 7069(2) Å3, Z = 4. Refinement was based on 3390 reflections and converged at a residual of 0.050. One form of {A figure is presented} (2) is isomorphous with 1a, crystallizing in the monoclinic space group P21/c, a = 19.840(3) Å, b = 16.445(3) Å, c = 24.074(4) Å, β = 112.39(1)°, V = 7264(1) Å3, Z = 4; refinement converged at a value of 0.060 for the conventional R factor. A second modification of (NBun 4)2[Mo4O8(OC2H5)2(NNC6H5)4] crystallizes in the tetragonal space group I41/a, a = 35.236(6) Å, b = 35.236(6) Å, c = 12.137(4) Å, V = 15066.0(13) Å3, Z = 8. Refinement based on 1734 reflections converged at a residual of 0.082. The structures consist of discrete tetranuclear units, presenting cis-bisdiazenido moieties, [Mo(NNC6H5)2]2+, bridged by two alkoxy groups and two tetra-oxomolybdate, [MoO4]2-, fragments.

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U2 - 10.1016/S0277-5387(00)84927-X

DO - 10.1016/S0277-5387(00)84927-X

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VL - 5

SP - 305

EP - 314

JO - Polyhedron

JF - Polyhedron

SN - 0277-5387

IS - 1-2

ER -