Hydrothermal Synthesis and Structural Characterization of Mixed-Valence Iron Phosphates: AFe5(PO4)5(OH)·H2O (A = Ca, Sr)

Edita Dvoncova, Kwang Hwa Lii

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19 Scopus citations

Abstract

Mixed-valence iron phosphates of the stoichiometry AFe5(PO4)5(OH)·H2O (A = Ca, Sr) have been synthesized hydrothermally and structurally characterized by single-crystal X-ray diffraction. Crystal data: CaFe5(PO4)5-(OH)·H2O, triclinic, P1̄, a = 6.404(1) Å, b = 7.866(1) Å, c = 15.694(2) Å, α = 85.00(1)∘, β = 88.79(1)∘, γ = 78.22(1)∘, V= 770.97(18) Å3, Z = 2, R = 0.034 for 2544 unique reflections; SrFe5(PO4)5(OH)·H2O, triclinic, P1̄, a = 6.4303(2) Å, b = 7.8749(8) Å, c = 15.894(2) Å, α = 84.75(1)∘, β = 87.96(1)∘, γ = 78.114(9)∘, V= 784.16(16) Å3, Z = 2, R = 0.0469 for 1854 unique reflections. The two compounds are isostructural. The complex framework consists of dimers of corner-sharing and edge-sharing FeIIIO6 octahedra joined through FeIIO5 trigonal bipyramids by corner- and edge-sharing, and discrete FeIIIO6 octahedra. Phosphate tetrahedra further knit together these Fe-O polyhedra by corner-sharing. Schlegel diagrams are used to help describe the arrangement of the next-nearest neighbors of the coordination polyhedra of Fe. The calcium ions are 7-coordinated and are located at intersections of the tunnels along the [010] and [110] directions. The structures are further defined by thermogravimetric and Mossbauer studies. Mossbauer spectroscopy confirms the presence of one FeII and four FeIII ions.

Original languageEnglish
Pages (from-to)4368-4372
Number of pages5
JournalInorganic Chemistry
Volume32
Issue number20
DOIs
StatePublished - 1993

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