Structure and magnetic properties of a new anion-deficient perovskite Pb2Ba2BiFe4ScO13 with crystallographic shear structure

Abstract

Pb2Ba2BiFe4ScO13, a new n=5 member of the oxygen-deficient perovskite-based AnBnO3n−2 homologous series, was synthesized using a solid-state method. The crystal structure of Pb2Ba2BiFe4ScO13 was investigated by a combination of synchrotron X-ray powder diffraction, electron diffraction, high-angle annular dark-field scanning transmission electron microscopy and Mössbauer spectroscopy. At 900K, it crystallizes in the Ammm space group with the unit cell parameters a=5.8459(1)Å, b=4.0426(1)Å, and c=27.3435(1)Å. In the Pb2Ba2BiFe4ScO13 structure, quasi-two-dimensional perovskite blocks are periodically interleaved with ½[110] (1¯ 0 1)p crystallographic shear (CS) planes. At the CS planes, the corner-sharing FeO6 octahedra are transformed into chains of edge-sharing FeO5 distorted tetragonal pyramids. B-positions of the perovskite blocks between the CS planes are jointly occupied by Fe3+ and Sc3+. The chains of the FeO5 pyramids and (Fe,Sc)O6 octahedra delimit six-sided tunnels that are occupied by double columns of cations with a lone electron pair (Pb2+). The remaining A-cations (Bi3+, Ba2+) occupy positions in the perovskite block. According to the magnetic susceptibility measurements, Pb2Ba2BiFe4ScO13 is antiferromagnetically ordered below TN ≈350K.