Structural investigations of the hexavanadium core {V6O19} in 'oxidized', mixed valence and 'reduced' clusters of the type [VV6-nVIVn O13-n(OH)n{(OCH2)3CR}2]2-, n=0, 3 and 6

Chen Qin, Jon Zubieta

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The reactions of [(n-C4H9)4N]3[H3V10O28] with the tris(hydroxymethyl)methane derived ligands (HOCH2)3CR yield hexavanadate clusters of the type [(n-C4H9)4N]2[V6O13{(OCH2)3CR}2] (R-NHC(O)CHCH2 (1) and -NO2 (1a)) and [C5H5NH]2[V6O13{(OCH2)3CCH3}2]·2Me2NCOH (2). These V(V) clusters are readily reduced by organohydrazines to yield the mixed valence V(V)/V(IV) cluster [(n-C4H9)4N]2[VV3VIV3O10(OH)3{(OCH2)3CNO2}2]·0.67CH2Cl2 (3) and the reduced V(IV) cluster [(n-C4H9)4N]2[VIV6O7(OH)6{(OCH2)3CCH3}2]·2HNPhNHPh (4). Complexes 1-4 share the common hexametalate core {M6O19} which is, however, distorted from the regular octahedral symmetry adopted by [Mo6O19]2- and [Nb6O19]8- because of the substitution of doubly-bridging oxo groups of the parent structure type by alkoxy donor oxygens and as a consequence of the reduction of metal sites in 3 and 4. Crystal data: 1, space group P21/c, a=10.602(3), b=17.774(5), c=16.451(6) Å, β=95.42(2)°, V=3086(2) Å3, Z=2, Dcalc=1.44 g/cm3; R=0.060 based on 2631 reflections. 2, orthorhombic Pbca,a=16.966(4), b=20.235(4), c=11.524(2) Å, V=3956(2) Å3, Z=4, Dcalc=1.77 g/cm3; R=0.034 based on 2729 reflections; 3, triclinic P1, a=13.526(2), b=27.032(5), c=12.950(2) Å, α=100.70(1), β=104.33(1), γ=75.56(1)°, V=4403(2) Å3, Z=3, Dcalc=1.52 g/cm3; R=0.058 based on 4494 reflections. 4, monoclinic P21/c, a=13.357(2), b=14.416(2), c=21.584(4) Å, β=105.83(2)°, V=3998(2) Å3, Z=2, Dcalc=1.33 g/cm3; R=0.058 based on 2972 reflections.

Original languageEnglish (US)
Pages (from-to)95-110
Number of pages16
JournalInorganica Chimica Acta
Issue numberC
StatePublished - 1992

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry
  • Materials Chemistry


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