Synthesis, structure and low temperature magnetism of the new lithium and sodium insertion compounds: LiFe(II)ClMoO4 and NaFe(II)ClMoO4

C. C. Torardi, W. M. Reiff, K. Lázár, E. Prince

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Abstract

The recently described tetragonal layered compound Fe(III)ClMoO4 is found to undergo reversible lithium and sodium ion insertion by stirring the solid in an acetonitrile solution of lithium or sodium iodide under argon. Reaction occurs via a topochemical redox-insertion mechanism where Fe3+ is reduced to Fe2+. LiFe(II)ClMoO4 is monoclinic with a = 6.9944(6), b = 6.8712(6), c = 5.0146(5) A ̊ and β = 91.270(5)° (space group P2I/m). NaFe(II)ClMoO4 appears to be orthorhombic with a = 7.174(2), b = 7.185(1) and c = 5.183(1) A ̊. The structure of LiFe(II)ClMoO4, determined by a Rietveld refinement of neutron powder diffraction data, is essentially the same as that of the precursor and contains Li ions in distorted octahedral sites between the layers. Also, the Fe atoms are shifted to a position where they are 6-coordinated compared to the 5-coordination observed in the ferric precursor. Zero field Mössbauer spectra for the lithium compound undergo hyperfine splitting that corresponds to a three-dimensional magnetic ordering process with TNéel∼ 68.5K. Low-dimensionality antiferromagnetism (probably one-dimensional chain in nature) is evident as a, broad maximum in the D.C. susceptibility at Tχmax ∼ 73 K. This is approximately 30 kelvins less than a similar low-dimensionality maximum observed in χm for the ferric precursor. Mössbauer spectra for the sodium insertion compound suggest cooperative three- dimensional magnetic order below ∼ 45 K.

Original languageEnglish
Pages (from-to)741-750
Number of pages10
JournalJournal of Physics and Chemistry of Solids
Volume47
Issue number8
DOIs
Publication statusPublished - 1986

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ASJC Scopus subject areas

  • Chemistry(all)
  • Materials Science(all)
  • Condensed Matter Physics

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