Abstract

Sr2Fe3Se2O3 is a localized-moment iron oxide selenide in which two unusual coordinations for Fe2+ ions form two sublattices in a 2:1 ratio. In the paramagnetic region at room temperature, the compound adopts the crystal structure first reported for Sr2Co3S2O3, crystallizing in space group Pbam with a = 7.8121 Å, b = 10.2375 Å, c = 3.9939 Å, and Z = 2. The sublattice occupied by two-thirds of the iron ions (Fe2 site) is formed by a network of distorted mer-[FeSe3O3] octahedra linked via shared Se2 edges and O vertices forming layers, which connect to other layers by shared Se vertices. As shown by magnetometry, neutron powder diffraction, and Mössbauer spectroscopy measurements, these moments undergo long-range magnetic ordering below TN1 = 118 K, initially adopting a magnetic structure with a propagation vector (1/2 - δ, 0, 1/2) (0 ≤ δ ≤ 0.1) which is incommensurate with the nuclear structure and described in the Pbam1 '( a01/2)000 s magnetic superspace group, until at 92 K ( TINC) there is a first order lock-in transition to a structure in which these Fe2 moments form a magnetic structure with a propagation vector (1/2, 0, 1/2) which may be modeled using a 2 a × b × 2 c expansion of the nuclear cell in space group 36.178 B a b21 m (BNS notation). Below TN2 = 52 K the remaining third of the Fe2+ moments (Fe1 site) which are in a compressed trans-[FeSe4O2] octahedral environment undergo long-range ordering, as is evident from the magnetometry, the Mössbauer spectra, and the appearance of new magnetic Bragg peaks in the neutron diffractograms. The ordering of the second set of moments on the Fe1 sites results in a slight reorientation of the majority moments on the Fe2 sites. The magnetic structure at 1.5 K is described by a 2 a × 2 b × 2 c expansion of the nuclear cell in space group 9.40 I a b (BNS notation).

Highlights

  • Multianion compounds adopt a diverse range of structures and have received recent attention in several contexts

  • The synthesis was modified by the inclusion of Fe2O3 and Fe to target (FeO)x(SrSe)y compositions with x > y to minimize impurities and infer the composition

  • Repeated annealing at 760 °C or below yielded a composition with higher levels of FeO or Fe3O4 impurity (∼2−5% by mass), whereas repeated annealing above 760 °C yielded a product with higher levels of SrFe2Se2O impurity (3−8% by mass)

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Summary

■ INTRODUCTION

Multianion compounds adopt a diverse range of structures and have received recent attention in several contexts. We used the X-ray diffractometer ID22 at the ESRF to investigate whether the magnetic ordering at TN2 gives rise to a small monoclinic distortion of the nuclear cell or the presence of 0 1/2 1/2 peaks that might be associated with the T′ transition in the heat capacity data of Lai et al.[15] Our measurement at 5 K showed no apparent symmetry lowering distortion (Figure S4), but a careful observation of the diffraction pattern indicated the presence of a very weak reflection, not present at ambient temperatures, that could be indexed as the 0 5/2 1/2 reflection (Figure S5) Even if this reflection is statistically significant, its spurious nature cannot be excluded, but its position and the propagation vector are consistent with the symmetry analysis. For discussion of the Mössbauer spectra at lower temperatures where Fe1 undergoes magnetic ordering the reader is referred to the data and analysis of Lai et al.[15]

■ CONCLUSIONS
■ ACKNOWLEDGMENTS
■ REFERENCES
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