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Topotactic synthesis and crystal structure of a highly fluorinated Ruddlesden-Popper-type iron oxide, Sr$$_{3}$$Fe$$_{2}$$O$$_{5+x}$$F$$_{2-x}$$ (x $${approx}$$ 0.44)

Tsujimoto, Yoshihiro*; Yamaura, Kazunari*; Hayashi, Naoaki*; Kodama, Katsuaki   ; Igawa, Naoki   ; Matsushita, Yoshitaka*; Katsuya, Yoshio*; Shirako, Yuichi*; Akaogi, Masaki*; Muromachi, Eiji*

Topotactic reaction of the Ruddlesden-Popper phase Sr$$_{3}$$Fe$$_{2}$$O$$_{7-delta}$$ ($$delta$$ $${approx}$$ 0.18) with polytetrafluoroethylene yields a highly fluorinated phase Sr$$_{3}$$Fe$$_{2}$$O$$_{5+x}$$F$$_{2-x}$$ (x $${approx}$$ 0.44), compared with Sr$$_{3}$$Fe$$_{2}$$O$$_{6}$$F$$_{0.87}$$ prepared by the reaction of Sr$$_{3}$$Fe$$_{2}$$O$$_{6}$$ and F$$_{2}$$ gas. Structure analyses based on powder neutron diffraction, synchrotron powder diffraction, and $$^{57}$$Fe M$"o$ssbauer spectroscopy measurements demonstrate that the new oxyfluoride perovskite has no anion deficiencies and adopts the tetragonal structure (space group ${it I}$4/${it mmm}$) with lattice constants ${it a}$ = 3.87264(6) ${AA}$ and ${it c}$ = 21.3465(6) ${AA}$ at room temperature. The fluoride ions preferentially occupy the terminal apical anion sites with oxide ions in a disordered manner, which results in square pyramidal coordination around iron.



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Category:Chemistry, Physical



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