Polyoxo Alkoxide Clusters of Vanadium: Structural Characterization of the Decavanadate Core in the “Fully Reduced” Vanadium(IV) Species [V10O16{(OCH2)3CCH2CH3}4]4− and [V10O16(OH)2{(OCH)2)3CCH2OH}4]2− and in the Mixed-Valence Clusters [VIV8VV2O16{(OCH2)3CR}4]2− (R = -CH2CH3, -CH3)

M. Ishaque Khan, Qin Chen, D. P. Goshorn, Jon Zubieta

Research output: Contribution to journalArticle

69 Scopus citations

Abstract

The hydrothermal reaction of a mixture of vanadium oxides with (HOCH2)3CCH2OH in the presence of Me3NHCl yields the reduced species (Me3NH)2[VIV10O14(OH)2{(OCH2)CCH2OH}4]·2H2O (1). In contrast, the reactions of vanadium oxides with (HOCH2)3CR3, using NaCl, KCl, or (C4H9)4NCl as mineralizers, yield the mixed-valence species M2[VIV8VV2O16{(OCH2)3CR}4]·nH2O (M = Na, n = 0, R = -CH2CH3 (2); ? = ?, n = 2, R = -CH2CH3 (3); M = (C4H9)4N, n = 0, R = -CH3 (4)). These compounds exhibit structures based on the decavanadate core {V10O28}, with ten doubly-bridging and two triply-bridging oxo groups of this parent structure replaced by the alkoxy donors of the ligands. The structural consequences of protonation of the core in 1 and of oxidation of two vanadium centers in 2-4 are presented. The crystal packing patterns of anion clusters and cations in these species reveal the common structural motif of anion stacking to produce polar and nonpolar channels. The influence of the cation on the details of the extended structure is apparent in the crystal packing descriptions. Crystal data are as follows. (Me3NH)2[V10O14(OH)2){(OCH2)3CCH2OH}4]-2H2O (1): monoclinic space group P21/c, a = 10.243(2) Å, b = 18.237(4) Å, c = 13.055(2) Å, β = 103.48(2)o, V = 2371.5(9) Å3, ? = 2, Dcalc = 1.95 g cm-3; structure solution and refinement based on 3505 reflections converged at R = 0.038. Na2[V10O16{(OCH2)3CCH2CH3}4] (2): monoclinic space group P21/c, a = 12.861(2) Å, b = 10.536(2) Å, c = 15.909(4) Å, β = 109.21(2)o, V= 2035.7(8) Å3, ? = 2, Dcalc = 2.18 g cm-3; 3006 reflections, R = 0.042. K2[V10O16{(OCH2)3CCH2CH3}4]-2H2O (3): triclinic space group P1̄, a = 10.249(2) Å, b = 12.438(2) Å, c = 9.903(2) Å, a = 97.51(1)o, β = 109.30(1)o, γ = 68.41(1)o, V = 1107.8(6) Å3, Dcalc = 2.10 g cm-3; 4441 reflections, R = 0.030. [(C4H9)4N]2[V10O16{(OCH2)3CCH3}4] (4): monoclinic space group, ?21/n, a = 13.523(4) Å, b= 18.453(3) Å, c = 14.375(6) Å, β= 104.87(2)o, V = 3466.9(15) Å3, ? = 2, Dcalc = 1.65 g cm-3; 2964 reflections, R = 0.047.

Original languageEnglish (US)
Pages (from-to)672-680
Number of pages9
JournalInorganic Chemistry
Volume32
Issue number5
DOIs
StatePublished - Jan 1 1993

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

Fingerprint Dive into the research topics of 'Polyoxo Alkoxide Clusters of Vanadium: Structural Characterization of the Decavanadate Core in the “Fully Reduced” Vanadium(IV) Species [V<sub>10</sub>O<sub>16</sub>{(OCH<sub>2</sub>)<sub>3</sub>CCH<sub>2</sub>CH<sub>3</sub>}<sub>4</sub>]<sup>4−</sup> and [V<sub>10</sub>O<sub>16</sub>(OH)<sub>2</sub>{(OCH)<sub>2</sub>)<sub>3</sub>CCH<sub>2</sub>OH}<sub>4</sub>]<sup>2−</sup> and in the Mixed-Valence Clusters [V<sup>IV</sup><sub>8</sub>V<sup>V</sup><sub>2</sub>O<sub>16</sub>{(OCH<sub>2</sub>)<sub>3</sub>CR}<sub>4</sub>]<sup>2−</sup> (R = -CH<sub>2</sub>CH<sub>3</sub>, -CH<sub>3</sub>)'. Together they form a unique fingerprint.

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