Crystal and Molecular Structure of a New Hexamolybdate-Cyclophosphazene Complex

Harry R. Allcock, E. C. Bissell, E. T. Shawl

Research output: Contribution to journalArticle

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Abstract

The reaction between molybdenum trioxide and hexakis(dimethylamino)cyclotriphosphazene, [NP(NMe2)2]3, in water yields yellow-green crystals of the salt [HN3P3(NMe2)6+]2[Mo6O192-] (I). Crystals of I are monoclinic with space group P21/C anda= 13.571 (13), b = 10.966 (11), c = 21.066 (19) A, β= 108.36 (6)°, Z = 2. A three-dimensional X-ray structure was determined by Patterson and Fourier methods with refinement by least-squares techniques to a conventional R factor of 0.029. The structure is characterized by the presence of puckered, ring-protonated cyclotriphosphazene structures in which long P-N skeletal bonds (1.663, 1.675 (5) A) and short skeletal bonds (1.560-1.599 (5) A) are found in the same ring. The N-P-N skeletal angles are in the range of 109.6-114.5 (3)° and the P-N-P angles are in the range of 126-129 (3)°. The Mo6O192- ion consists of a slightly distorted cage of six molybdenum atoms located octahedrally around a central oxygen atom, with twelve oxygen atoms disposed in Mo-O-Mo units and one terminal oxygen attached to each molybdenum. The terminal Mo-O bond distances have a range of 1.676-1.678 (5) A, while the bridge Mo-O bonds have lengths within the range of 1.855-2.005 (4) A. The central Mo-O bond lengths are in the range of 2.312-2.324 (4) A. This constitutes the first X-ray structural identification of the Mo6O192- system.

Original languageEnglish (US)
Pages (from-to)2963-2968
Number of pages6
JournalInorganic Chemistry
Volume12
Issue number12
DOIs
StatePublished - Dec 1 1973

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Molecular structure
molybdenum
molecular structure
Molybdenum
Crystal structure
Bond length
Oxygen
Atoms
crystal structure
oxygen atoms
X rays
Crystals
R Factors
rings
crystals
x rays
Salts
Ions
salts
Water

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

Cite this

Allcock, Harry R. ; Bissell, E. C. ; Shawl, E. T. / Crystal and Molecular Structure of a New Hexamolybdate-Cyclophosphazene Complex. In: Inorganic Chemistry. 1973 ; Vol. 12, No. 12. pp. 2963-2968.
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title = "Crystal and Molecular Structure of a New Hexamolybdate-Cyclophosphazene Complex",
abstract = "The reaction between molybdenum trioxide and hexakis(dimethylamino)cyclotriphosphazene, [NP(NMe2)2]3, in water yields yellow-green crystals of the salt [HN3P3(NMe2)6+]2[Mo6O192-] (I). Crystals of I are monoclinic with space group P21/C anda= 13.571 (13), b = 10.966 (11), c = 21.066 (19) A, β= 108.36 (6)°, Z = 2. A three-dimensional X-ray structure was determined by Patterson and Fourier methods with refinement by least-squares techniques to a conventional R factor of 0.029. The structure is characterized by the presence of puckered, ring-protonated cyclotriphosphazene structures in which long P-N skeletal bonds (1.663, 1.675 (5) A) and short skeletal bonds (1.560-1.599 (5) A) are found in the same ring. The N-P-N skeletal angles are in the range of 109.6-114.5 (3)° and the P-N-P angles are in the range of 126-129 (3)°. The Mo6O192- ion consists of a slightly distorted cage of six molybdenum atoms located octahedrally around a central oxygen atom, with twelve oxygen atoms disposed in Mo-O-Mo units and one terminal oxygen attached to each molybdenum. The terminal Mo-O bond distances have a range of 1.676-1.678 (5) A, while the bridge Mo-O bonds have lengths within the range of 1.855-2.005 (4) A. The central Mo-O bond lengths are in the range of 2.312-2.324 (4) A. This constitutes the first X-ray structural identification of the Mo6O192- system.",
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Crystal and Molecular Structure of a New Hexamolybdate-Cyclophosphazene Complex. / Allcock, Harry R.; Bissell, E. C.; Shawl, E. T.

In: Inorganic Chemistry, Vol. 12, No. 12, 01.12.1973, p. 2963-2968.

Research output: Contribution to journalArticle

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N2 - The reaction between molybdenum trioxide and hexakis(dimethylamino)cyclotriphosphazene, [NP(NMe2)2]3, in water yields yellow-green crystals of the salt [HN3P3(NMe2)6+]2[Mo6O192-] (I). Crystals of I are monoclinic with space group P21/C anda= 13.571 (13), b = 10.966 (11), c = 21.066 (19) A, β= 108.36 (6)°, Z = 2. A three-dimensional X-ray structure was determined by Patterson and Fourier methods with refinement by least-squares techniques to a conventional R factor of 0.029. The structure is characterized by the presence of puckered, ring-protonated cyclotriphosphazene structures in which long P-N skeletal bonds (1.663, 1.675 (5) A) and short skeletal bonds (1.560-1.599 (5) A) are found in the same ring. The N-P-N skeletal angles are in the range of 109.6-114.5 (3)° and the P-N-P angles are in the range of 126-129 (3)°. The Mo6O192- ion consists of a slightly distorted cage of six molybdenum atoms located octahedrally around a central oxygen atom, with twelve oxygen atoms disposed in Mo-O-Mo units and one terminal oxygen attached to each molybdenum. The terminal Mo-O bond distances have a range of 1.676-1.678 (5) A, while the bridge Mo-O bonds have lengths within the range of 1.855-2.005 (4) A. The central Mo-O bond lengths are in the range of 2.312-2.324 (4) A. This constitutes the first X-ray structural identification of the Mo6O192- system.

AB - The reaction between molybdenum trioxide and hexakis(dimethylamino)cyclotriphosphazene, [NP(NMe2)2]3, in water yields yellow-green crystals of the salt [HN3P3(NMe2)6+]2[Mo6O192-] (I). Crystals of I are monoclinic with space group P21/C anda= 13.571 (13), b = 10.966 (11), c = 21.066 (19) A, β= 108.36 (6)°, Z = 2. A three-dimensional X-ray structure was determined by Patterson and Fourier methods with refinement by least-squares techniques to a conventional R factor of 0.029. The structure is characterized by the presence of puckered, ring-protonated cyclotriphosphazene structures in which long P-N skeletal bonds (1.663, 1.675 (5) A) and short skeletal bonds (1.560-1.599 (5) A) are found in the same ring. The N-P-N skeletal angles are in the range of 109.6-114.5 (3)° and the P-N-P angles are in the range of 126-129 (3)°. The Mo6O192- ion consists of a slightly distorted cage of six molybdenum atoms located octahedrally around a central oxygen atom, with twelve oxygen atoms disposed in Mo-O-Mo units and one terminal oxygen attached to each molybdenum. The terminal Mo-O bond distances have a range of 1.676-1.678 (5) A, while the bridge Mo-O bonds have lengths within the range of 1.855-2.005 (4) A. The central Mo-O bond lengths are in the range of 2.312-2.324 (4) A. This constitutes the first X-ray structural identification of the Mo6O192- system.

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