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X-ray and Neutron Diffraction Studies of SrTe(2)FeO(6)Cl, an Oxide Chloride with Rare Anion Ordering

[Image: see text] The oxychloride SrTe(2)FeO(6)Cl is obtained by high-temperature solid-state synthesis under inert conditions in closed reaction vessels. The compound crystallizes in a novel monoclinic crystal structure that is described in the space group P12(1)/n1 (No. 14). The unit cell paramete...

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Autores principales: Sannes, Johnny A., Gonano, Bruno, Fjellvåg, Øystein S., Kumar, Susmit, Nilsen, Ola, Valldor, Martin
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2023
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10428212/
https://www.ncbi.nlm.nih.gov/pubmed/37531570
http://dx.doi.org/10.1021/acs.inorgchem.3c01951
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author Sannes, Johnny A.
Gonano, Bruno
Fjellvåg, Øystein S.
Kumar, Susmit
Nilsen, Ola
Valldor, Martin
author_facet Sannes, Johnny A.
Gonano, Bruno
Fjellvåg, Øystein S.
Kumar, Susmit
Nilsen, Ola
Valldor, Martin
author_sort Sannes, Johnny A.
collection PubMed
description [Image: see text] The oxychloride SrTe(2)FeO(6)Cl is obtained by high-temperature solid-state synthesis under inert conditions in closed reaction vessels. The compound crystallizes in a novel monoclinic crystal structure that is described in the space group P12(1)/n1 (No. 14). The unit cell parameters, a = 10.2604(1) Å, b = 5.34556(5) Å, c = 26.6851(3) Å, and β = 93.6853(4)°, and atomic parameters were determined from synchrotron diffraction data, starting from a model that was obtained from single-crystal X-ray diffraction data. The anion lattice exhibits a rare ordering of oxide and chloride ions: one-dimensional zig-zag ladders of chlorine (squarelike motif) are surrounded by an oxygen matrix. Two different iron sites coordinated solely to oxygen are present in the structure, one octahedral and one square pyramidal, both distorted. Similarly, two different strontium coordinations are present; the first homoleptic coordinated to eight oxygen atoms and the second heteroleptic coordinated to four oxygen and four chlorine atoms in a fac-like manner. The lone pair of Te(IV) is directed toward the larger chlorine atoms. Magnetic susceptibility measurements confirm that Fe is +3 (d(5)) in the high-spin electronic configuration, exhibiting an almost ideal spin-only moment, μ(eff) = 5.65 μ(B) Fe(–1). The slightly negative Weiss constant (θ(CW) = −39 K) suggests dominating antiparallel spin-to-spin coupling in the paramagnetic temperature range, agreeing with an observed long-range antiferromagnetic spin ordering below Néel temperature, T(N) ∼ 13 K, and a broad second order-like anomaly in the specific heat measurement data. Low-temperature neutron diffraction data reveal that the antiferromagnetic ordered phase is C-type, with a k-vector (1/2, 1/2, 0) and ordered moment of 4.14(7) μ(B). The spin structure can be described as antiferromagnetic ordered layers stacked along the a-axis, forming layers of squares that alternate along the c-axis.
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spelling pubmed-104282122023-08-17 X-ray and Neutron Diffraction Studies of SrTe(2)FeO(6)Cl, an Oxide Chloride with Rare Anion Ordering Sannes, Johnny A. Gonano, Bruno Fjellvåg, Øystein S. Kumar, Susmit Nilsen, Ola Valldor, Martin Inorg Chem [Image: see text] The oxychloride SrTe(2)FeO(6)Cl is obtained by high-temperature solid-state synthesis under inert conditions in closed reaction vessels. The compound crystallizes in a novel monoclinic crystal structure that is described in the space group P12(1)/n1 (No. 14). The unit cell parameters, a = 10.2604(1) Å, b = 5.34556(5) Å, c = 26.6851(3) Å, and β = 93.6853(4)°, and atomic parameters were determined from synchrotron diffraction data, starting from a model that was obtained from single-crystal X-ray diffraction data. The anion lattice exhibits a rare ordering of oxide and chloride ions: one-dimensional zig-zag ladders of chlorine (squarelike motif) are surrounded by an oxygen matrix. Two different iron sites coordinated solely to oxygen are present in the structure, one octahedral and one square pyramidal, both distorted. Similarly, two different strontium coordinations are present; the first homoleptic coordinated to eight oxygen atoms and the second heteroleptic coordinated to four oxygen and four chlorine atoms in a fac-like manner. The lone pair of Te(IV) is directed toward the larger chlorine atoms. Magnetic susceptibility measurements confirm that Fe is +3 (d(5)) in the high-spin electronic configuration, exhibiting an almost ideal spin-only moment, μ(eff) = 5.65 μ(B) Fe(–1). The slightly negative Weiss constant (θ(CW) = −39 K) suggests dominating antiparallel spin-to-spin coupling in the paramagnetic temperature range, agreeing with an observed long-range antiferromagnetic spin ordering below Néel temperature, T(N) ∼ 13 K, and a broad second order-like anomaly in the specific heat measurement data. Low-temperature neutron diffraction data reveal that the antiferromagnetic ordered phase is C-type, with a k-vector (1/2, 1/2, 0) and ordered moment of 4.14(7) μ(B). The spin structure can be described as antiferromagnetic ordered layers stacked along the a-axis, forming layers of squares that alternate along the c-axis. American Chemical Society 2023-08-02 /pmc/articles/PMC10428212/ /pubmed/37531570 http://dx.doi.org/10.1021/acs.inorgchem.3c01951 Text en © 2023 The Authors. Published by American Chemical Society https://creativecommons.org/licenses/by/4.0/Permits the broadest form of re-use including for commercial purposes, provided that author attribution and integrity are maintained (https://creativecommons.org/licenses/by/4.0/).
spellingShingle Sannes, Johnny A.
Gonano, Bruno
Fjellvåg, Øystein S.
Kumar, Susmit
Nilsen, Ola
Valldor, Martin
X-ray and Neutron Diffraction Studies of SrTe(2)FeO(6)Cl, an Oxide Chloride with Rare Anion Ordering
title X-ray and Neutron Diffraction Studies of SrTe(2)FeO(6)Cl, an Oxide Chloride with Rare Anion Ordering
title_full X-ray and Neutron Diffraction Studies of SrTe(2)FeO(6)Cl, an Oxide Chloride with Rare Anion Ordering
title_fullStr X-ray and Neutron Diffraction Studies of SrTe(2)FeO(6)Cl, an Oxide Chloride with Rare Anion Ordering
title_full_unstemmed X-ray and Neutron Diffraction Studies of SrTe(2)FeO(6)Cl, an Oxide Chloride with Rare Anion Ordering
title_short X-ray and Neutron Diffraction Studies of SrTe(2)FeO(6)Cl, an Oxide Chloride with Rare Anion Ordering
title_sort x-ray and neutron diffraction studies of srte(2)feo(6)cl, an oxide chloride with rare anion ordering
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10428212/
https://www.ncbi.nlm.nih.gov/pubmed/37531570
http://dx.doi.org/10.1021/acs.inorgchem.3c01951
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