Hydrothermal Synthesis, Structural Characterization, and Physical Properties of a New Mixed Valence Iron Phosphate, SrFe3(PO4)3

✍ Scribed by Michael B. Korzenski; Joseph W. Kolis; Gary J. Long

• Publisher: Elsevier Science
• Year: 1999
• Tongue: English
• Weight: 230 KB
• Volume: 147
• Category: Article
• ISSN: 0022-4596
• DOI: 10.1006/jssc.1999.8392

✦ Synopsis

A new mixed valence Fe(II/III) phosphate, SrFe 3 (PO 4 ) 3 , has been synthesized hydrothermally and structurally characterized by single-crystal X-ray di4raction, EDAX, magnetic susceptibility, Mo] ssbauer, infrared and di4use re6ectance spectroscopies, DTA, and bond valence sum calculations. The compound crystallizes in the orthorhombic space group Imma (No. 74) with a‫,)3(254.01؍‬ b‫,)3(924.31؍‬ c‫)2(825.6؍‬ A s s , V‫)4(3.619؍‬ A s s 3 and Z‫4؍‬ with R/R w ‫.7030.0/7020.0؍‬ The structure consists of a complex low-dimensional framework constructed of FeO 6 octahedra and PO 4 tetrahedra that form 2D channels in which the strontium ions are located. The framework contains two simple building blocks: rigid columns of edge-sharing Fe 2 P 2 O 14 units and zigzag chains of alternating PO 4 +FeO 6 +PO 4 units, both of which run parallel to the b direction. This linkage forms intersecting channels which run parallel to the a and b axes. The divalent strontium cations reside within these channels and create openings in the ab plane with dimensions of 6.903(4) and 7.469(4) A s s , respectively. These openings can easily accommodate both small and large monovalent or divalent cations, as demonstrated by several cation exchange reactions. The MoK ssbauer spectral parameters are consistent with the structure and reveal the presence of mixed valent octahedral iron(II) and iron(III) sites in the expected two to one ratio. The quadrupole splittings observed for both iron sites are very large as is expected for the very asymmetric coordination environments found for each iron site.