Hydrothermal syntheses and structures of reduced and mixed valence polyoxovanadium clusters with capped cage cores:...

M. Ishaque Khan, Qin Chen, Jon Zubieta

Research output: Contribution to journalArticle

64 Scopus citations

Abstract

Title full: Hydrothermal syntheses and structures of reduced and mixed valence polyoxovanadium clusters with capped cage cores: K3[H12(AsO)2(AsO4)V6 IVV6VO36] ·12H2O and Rb5 [(As2O)4(VO)2V12IV O36Cl]·2H2O. The reaction of NaVO3, As2O3, KSCN, H2NC(CH2OH)3, H2SO4 and H2O yielded black crystals of K3[H12(AsO)2(AsO4)V12 O36]·12H2O (1). The structure of 1 consists of a {(AsO4)V12O36} α-Keggin core capped on two tetragonal faces by {AsO} units. Crystal data for H36O54K3V12As3: cubic space group Pm3m, a=10.583(2) Å, V=1185.3(9) Å3, Z=1, Dcalc=2.664 g cm-3. Structure solution and refinement based on 193 reflections with Io≥3σ(Io) converged at a discrepancy value of 0.0628. The hydrothermal reaction of a mixture of V2O5, V2O3, V (-325 mesh), H5As3O10, RbOH and H2O in the mole ratio 5:5:5:3:6.4:333 for 60 h at 200 °C produced lustrous black crystals of Rb5[As8V14O42Cl]·2H 2O (2). The structure of 2 is similar to those of the general class of 'reduced' or V(IV) clusters of the type [V(18-p)As2pO42(X)]m-, where X=SO3, SO4, H2O and p=3, 4, which are topologically related to the elongated square gyrobicupola and extended cage core of [V18O42(X)]n-. Thus, the structure of 2 is constructed from the framework of 24 bridging oxo groups by the capping of four tetragonal faces by {As2O} groups and of fourteen faces by {VO} groups and by encapsulation of a Cl-anion. Crystal data for As8ClH4O44Rb5V14: monoclinic P21, a=13.141(2), b=13.525(2), c=13.412(2) Å, β=92.59(1)°, V=2381.3(12) Å3, Z=2, Dcalc=3.46 g cm-3. Structure solution and refinement based on 4518 reflections with Io ≥3σ(Io) converged at R=0.0623.

Original languageEnglish (US)
Pages (from-to)199-206
Number of pages8
JournalInorganica Chimica Acta
Volume212
Issue number1-2
DOIs
StatePublished - Oct 1993

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry
  • Materials Chemistry

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