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Synthesis, Crystal Structure, and Optical Properties of Layered Perovskite Scandium Oxychlorides: Sr2ScO3Cl, Sr3Sc2O5Cl2, and Ba3Sc2O5Cl2
journal contribution
posted on 2018-04-19, 12:04 authored by Yu Su, Yoshihiro Tsujimoto, Kotaro Fujii, Makoto Tatsuta, Kengo Oka, Masatomo Yashima, Hiraku Ogino, Kazunari YamauraWe
report the successful synthesis of three new Ruddlesden–Popper-type
scandium oxychloride perovskites, Sr2ScO3Cl, Sr3Sc2O5Cl2, and Ba3Sc2O5Cl2, by conventional solid-state reaction. Small single crystals of
Sr2ScO3Cl were obtained by a self-flux
method, and the crystal structure was determined to belong to the
tetragonal P4/nmm space group (a = 4.08066(14) Å, c = 14.1115(8)
Å) by X-ray diffraction analysis. The scandium center forms a
ScO5Cl octahedron with ordered apical oxygen and chlorine
anions. The scandium cation, however, is shifted from the position
of the octahedral center toward the apical oxygen anion, such that
the coordination geometry of the Sc cation can be effectively viewed
as an ScO5 pyramid. These structural features in the oxychloride
are different from those of octahedral ScO5F coordinated
with a partial O/F anion order at the apical sites in the oxyfluoride
Sr2ScO3F. Rietveld refinements of the
neutron powder diffraction data of Sr3Sc2O5Cl2 (I4/mmm: a = 4.107982(5) Å, c = 23.58454(7)
Å) and Ba3Sc2O5Cl2 (I4/mmm: a = 4.206920(5) Å, c = 24.54386(6) Å) reveal
the presence of pseudo ScO5 pyramids with the Cl anion
being distant from the scandium cation, which is similar to the Sc-centered
coordination geometry in Sr2ScO3Cl with
the exception that the ScO5 pyramids form double layers
by sharing the apical oxygen. Density functional calculations on Sr2ScO3Cl indicate the strong covalency of the
Sc–O bonds but almost nonbonding interaction between Sc and
Cl ions.
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Keywords
ScO 5 pyramidsSc-centered coordination geometryapical oxygen anionSr 2 ScO 3 Clneutron powder diffraction dataBa 3 Sc 2 O 5 Cl 2X-ray diffraction analysisoctahedral ScO 5 FScO 5 Cl octahedronapical oxygenSr 3 Sc 2 O 5 Cl 2scandium cationLayered Perovskite Scandium Oxychloridesscandium center formsScO 5 pyramidScO 5 pyramids form
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