A 3-D Organically Templated Mixed Valence (Fe2+/Fe3+) Iron Phosphate with Oxide-Centered Fe4O(PO4)4 Cubes: Hydrothermal Synthesis, Crystal Structure, Magnetic Susceptibility, and Mössbauer Spectroscopy of [H3NCH2CH2NH3]2[Fe 4O(PO4)4]·H2O

Jeffrey R.D. DeBord, William M. Reiff, Christopher J. Warren, Robert C. Haushalter, Jon Zubieta

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A 3-D, open framework, mixed valence iron phosphate, [H3NCH2CH2NH3]2[Fe 4O-(PO4)4]·H2O, which contains organic ethylenediammonium dications in the framework voids, has been prepared via hydrothermal synthesis and has been characterized by single-crystal X-ray diffraction, magnetic susceptibility, and variable temperature Mössbauer spectroscopy. Crystal data: tetragonal, space group I42m with a = 10.1383(8) Å, c = 9.628(1) Å, V = 989.6(1) Å3, Z = 2, and R(RW) = 7.7(6.5) for 276 reflections (I > 3σ(I)) and 32 variables. The fundamental building block of the structure is a novel cubane-like cluster with trigonal bipyramidal iron and tetrahedral phosphorus atoms lying at alternate vertexes of a cube with a tetrahedrally coordinated oxygen atom at the center of the cube. Each cluster is linked by eight Fe-O-P bonds that extend along what would be all 〈111〉 directions of the putative cube to eight similar clusters to form a framework that is only slightly distorted (by the presence of the organic cations) from cubic 43m symmetry. Mössbauer and ac magnetic susceptibility measurements show that equal amounts of valence trapped Fe2+ and Fe3+ are present, which undergo long range magnetic ordering at ∼12 K.

Original languageEnglish (US)
Pages (from-to)1994-1998
Number of pages5
JournalChemistry of Materials
Issue number9
StatePublished - Sep 1 1997


ASJC Scopus subject areas

  • Chemistry(all)
  • Chemical Engineering(all)
  • Materials Chemistry

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