Synthesis and characterization of two vanadium chalcogenides, [NH 4][H(VO)(SeO3)2] and Cs4[(VOS 2)2(μ-O)], prepared solvothermally

Mehtap Emirdag-Eanes, James A. Ibers*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

4 Scopus citations

Abstract

The new compounds [NH4][H(VO)(SeO3)2] and Cs4[(VOS2)2(μ-O)] have been synthesized solvothermally at 170 °C. [NH4][H(VO)(SeO3) 2] was synthesized by the hydrothermal reaction of V and Na 2Se with NH4Cl as mineralizer. The compound crystallizes in the space group P21/m of the monoclinic system with four formula units in a cell of dimensions a=3.9883(13) Å, b=10.504(3) Å, c=7.953(3) Å, β=98.571(5)°, V=329.45(19) Å3 (T=153 K). The structure is composed of linear chains of repeating [(VO)(SeO3)2]2- units, similar to those found in K[H(VO)(SeO3)2]. NH4+ ions reside among the chains and take part in an extensive hydrogen bonding scheme. The H center is involved in a very short, apparently symmetric, O-H-O hydrogen bond 2.479(6) Å in length. The compound displays Curie-Weiss paramagnetism in the range 30-300 K with μeff=1.796(5) μ B, in close agreement with the theoretical spin-only effective moment expected for V4+. There is antiferromagnetic coupling below 20 K. Cs4[(VOS2)2(μ-O)] was synthesized by the methanothermal reaction of V and Cs2S3. It crystallizes in the space group Pnma of the orthorhombic system with four formula units in a cell of dimensions a=13.3280(15) Å, b=8.7912(10) Å, c=12.2140(14) Å, V=1431.1(3) Å3 (T=153 K). Cs4[(VOS2)2(μ-O)] appears to be the first mixed O/S pyrovanadate structure type. Each of the V5+ centers is tetrahedrally coordinated by an O and two S atoms as well as by another O atom that is corner-shared between the two tetrahedra. Cs+ ions reside among the [(VOS2)2(μ-O)]4- units.

Original languageEnglish (US)
Pages (from-to)66-70
Number of pages5
JournalJournal of Alloys and Compounds
Volume361
Issue number1-2
DOIs
StatePublished - Oct 27 2003

Keywords

  • Chalcogenides
  • X-ray diffraction

ASJC Scopus subject areas

  • Mechanics of Materials
  • Mechanical Engineering
  • Metals and Alloys
  • Materials Chemistry

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