Synthesis, structure, magnetic susceptibility and Mössbauer and Raman spectroscopies of the new oxyphosphate Fe0.50TiO(PO4)

A new iron titanyl oxyphosphate Fe{sub 0.50}TiO(PO{sub 4}) was synthesized by both solid-state reaction and Cu{sup 2+}-Fe{sup 2+} ion exchange method. The material was then characterized by X-ray diffraction, Mossbauer spectroscopy, magnetic susceptibility measurements and Raman spectroscopy. The crystal structure of the compound was refined, using X-ray powder diffraction data, by Rietveld profile method; it crytallizes in the monoclinic system, space group P2{sub 1}/c (No.14), with a=7.4039(3)A, b=7.3838(3)A, c=7.4083(3)A, {beta}=120.36{sup o}(1), V=349.44(2)A{sup 3} and Z=4. The volume of the title compound is comparable to those of the M{sub 0.50}{sup II}TiO(PO{sub 4}) series, where M{sup II}=Mg, Co, Ni and Zn. The framework is built up from [TiO{sub 6}] octahedra and [PO{sub 4}] tetrahedra. [TiO{sub 6}] octahedra are linked together by corners and form infinite chains along the c-axis. Ti atoms are displaced from the center of octahedral units showing an alternating short distance (1.73A) and a long one (2.22A). These chains are linked together by [PO{sub 4}] tetrahedra. Fe{sup 2+} cations occupy a triangle-based antiprism sharing two faces with two [TiO{sub 6}] octahedra. Mossbauer and magnetic measurements show the existence of iron only in divalent state, located exclusively in octahedral sites with high spin confition (t{sub 2g}{sup 4}e{sub g}{sup 2}). Ramanmore » study confirms the existence of Ti-O-Ti chains.« less