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Structural Distortions and Magnetic Ordering in Ae2FeO3CuCh (Ae = Ca, Sr; Ch = S, Se) Oxide Chalcogenides
Robert D Smyth1, Bradley C Sheath1, Lemuel E Crentsil1
1Department of Chemistry, Inorganic Chemistry Laboratory, University of Oxford, South Parks Road, Oxford OX1 3QR, U.K.
Abstract:
The contrasting crystal and magnetic structures of four related iron oxide chalcogenides are reported. Ae2FeO3CuCh (Ae = Ca, Sr; Ch = S, Se) all crystallize in the Sr2GaO3CuS structure with alkaline earth iron oxide layers containing double layers of linked FeO5 square pyramids containing Fe3+ ions separated by antifluorite-type [Cu2Ch2]2- layers. Structural distortions occur below room temperature when the small Ca2+ ions are present, and these involve cooperative tilting of the FeO5 square pyramids. Magnetic reflections present in the diffraction patterns can be indexed using either √2a × √2a × c or √2a × √2a × 2c expansions of the nuclear cell with nearest-neighbor Fe3+ moments coupling antiferromagnetically and with temperature-dependent orientations relative to the crystallographic directions. The magnetic structures of these compounds are subtly different in detail, partly on account of the low directional preference of the high-spin d5 Fe3+ moments.
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