Surface complexation of [Nb6O19]8- with NiII: Solvothermal synthesis and X-ray structural characterization of two novel heterometallic Ni-Nb-polyoxometalates

Kaspar Hegetschweiler, Robert C. Finn, Randy S. Rarig, Jürgen Sander, Stefan Steinhauser, Michael Wörle, Jon Zubieta

Research output: Contribution to journalArticle

37 Scopus citations

Abstract

Solvothermal reaction of NiCl2, Nb(OEt)5 and 1,3,5-triamino-1,3,5-trideoxy-cis-inositol (taci) in a 1:1:1 ratio under alkaline conditions (NaOH) resulted in the formation of two new Nb-Ni heteropolyoxometalate complexes. [Ni(taci)2]2{trans-[Nb6O19][Ni (taci)]2}·26H2O (1) and [Na(H2O)6]2{cis-[H2Nb 6O19][Ni(taci)]2}·18H2O (2), were characterized by single crystal X-ray analysis. In both compounds, two [Ni(taci)]2+ entities are each bonded to three Nb-O-Nb bridges of a central Nb6O19 unit, resulting in the formation of an approximately C3v symmetric NiN3O3 coordination geometry. The mononuclear analogue [Ni(taci)(H2O)3]2+ was crystallized as the sulfate and structurally characterized for comparison. The two isolated anions {trans-[Nb6O19][Ni(taci)]2}4- and {cis-[H2Nb6O19][Ni(taci)]2} 2- have approximate D3d and C2v symmetry, respectively. Compound 2 crystallized, however, in the cubic space group Pn3̄m (No. 224) with the two Ni centers equally distributed over four symmetry equivalent sites. In this structure, the [Na(H2O)6]+ cations and the {cis-[H2Nb6O19][Ni(taci)]2} 2- anions represent linearly and tetrahedrally connecting building blocks in a hydrogen bonded supramolecular architecture which can be described in terms of two independent but interpenetrating diamond-type nets.

Original languageEnglish (US)
Pages (from-to)39-47
Number of pages9
JournalInorganica Chimica Acta
Volume337
DOIs
StatePublished - Sep 26 2002

Keywords

  • Hexaniobates
  • Hydrogen bonding
  • Nickel complexes
  • Solvothermal synthesis
  • Supramolecular structures

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry
  • Materials Chemistry

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