Hydrothermal Synthesis and Characterization of Hexavanadium Polyoxo Alkoxide Anion Clusters: Crystal Structures of the Vanadium(IV) Species Ba[V6O7(OH)3{(OCH2)3CCH3}3]·3H2O and Na2[V6O7{(OCH2)3CCH2CH3}4], of the Mixed-Valence Complex (Me3NH)[VIV5VVO7(OH)3{(OCH2)3CCH3}3], and of the Fluoro Derivative Na[V6O6F(OH)3{(OCH2)3CCH3}3]·3H2O

M. Ishaque Khan, Qin Chen, Hakon Höpe, Sean Parkin, Charles J. O'Connor, Jon Zubieta

Research output: Contribution to journalArticle

77 Scopus citations

Abstract

The hydrothermal reactions of vanadium oxide precursors with trialkoxy ligands of the class (HOCH2)3CR (R = CH3, CH2CH3) yield polyalkoxyoxovanadium clusters with a hexametalate core, Ba[V6O7(OH)3{(OCH2)3CCH3}3]·3H2O (1), Na2[V6O7{(OCH2)3CCH2CH3}4] (2), (Me3NH)[V6O7(OH)3{(OCH2)3CCH3}3] (3), and Na[V6O6F(OH)3{(OCH2)3CCH3}3]·3H2O (4). Cluster 1 is a fully-reduced V(IV) species in which nine doubly bridging oxo groups of the parent {V6O19} core have been substituted by alkoxy oxygen donors of the three trialkoxy ligands. The structure of 3 is grossly similar to that of 1, with differences in metrical parameters reflecting the presence of one oxidized V(V) site in the metal core of 3. The fully reduced cluster 2 exhibits complete substitution of the doubly-bridging oxo groups of the parent core by 12 ligand alkoxy donors. The tendency of polyvanadium oxide clusters to encapsulate a variety of guest molecules or ions is demonstrated by the structure of 4, in which the central μ6-oxo group of the parent core has been substituted by a μ3-fluoride, resulting in a considerably distorted {V6O6-(μ3-F)(μ2-OH)32-OR)9} core. Crystal data for 1: hexagonal space group P63mc, a = 13.707(1) Å, c = 9.647(2) Å, V = 1569.7(2) Å3, Z = 2, Dcalc = 2.140 g cm−3; structure solution and refinement based on 399 reflections converged at R = 0.0576. Crystal data for 2: cubic space group Fd3, a = 19.202(4) Å, V= 7080(1) Å3, Z = 8, Dcalc = 1.749 g cm−3; 293 reflections, R = 0.0509. Crystal data for 3: hexagonal space group P63mc, a = 12.792(3) Å, c = 10.692(2) Å, V= 1515.2(6) Å3, Z = 2, Dcalc = 1.929 g cm−3; 651 reflections, R = 0.0410. Crystal data for 4: hexagonal space group P63mc, a = 12.977(1) Å, c = 10.160(1) Å, V= 1481.7(2) Å3, Z = 2, Dcalc = 2.020 g cm−3; 379 reflections, R = 0.0371.

Original languageEnglish (US)
Pages (from-to)2929-2937
Number of pages9
JournalInorganic Chemistry
Volume32
Issue number13
DOIs
StatePublished - Jan 1 1993

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

Fingerprint Dive into the research topics of 'Hydrothermal Synthesis and Characterization of Hexavanadium Polyoxo Alkoxide Anion Clusters: Crystal Structures of the Vanadium(IV) Species Ba[V<sub>6</sub>O<sub>7</sub>(OH)<sub>3</sub>{(OCH<sub>2</sub>)<sub>3</sub>CCH<sub>3</sub>}<sub>3</sub>]·3H<sub>2</sub>O and Na<sub>2</sub>[V<sub>6</sub>O<sub>7</sub>{(OCH<sub>2</sub>)<sub>3</sub>CCH<sub>2</sub>CH<sub>3</sub>}<sub>4</sub>], of the Mixed-Valence Complex (Me<sub>3</sub>NH)[V<sup>IV</sup><sub>5</sub>V<sup>V</sup>O<sub>7</sub>(OH)<sub>3</sub>{(OCH<sub>2</sub>)<sub>3</sub>CCH<sub>3</sub>}<sub>3</sub>], and of the Fluoro Derivative Na[V<sub>6</sub>O<sub>6</sub>F(OH)<sub>3</sub>{(OCH<sub>2</sub>)<sub>3</sub>CCH<sub>3</sub>}<sub>3</sub>]·3H<sub>2</sub>O'. Together they form a unique fingerprint.

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