000170200 001__ 170200
000170200 005__ 20260407115449.0
000170200 0247_ $$2doi$$a10.1039/d6cc00150e
000170200 0248_ $$2sideral$$a148735
000170200 037__ $$aART-2026-148735
000170200 041__ $$aeng
000170200 100__ $$aGillette, Alexis N.
000170200 245__ $$aStructure and magnetism of mixed-valent iron oxysulfides Sr3Fe4O6S2 (Sr3(Fe3+)2O5(Fe2+)2OS2) and Sr4Fe4O7S2 (Sr4(Fe3+)2O6(Fe2+)2OS2)
000170200 260__ $$c2026
000170200 5060_ $$aAccess copy available to the general public$$fUnrestricted
000170200 5203_ $$aThe crystal and magnetic structures of Sr3Fe4O6S2 ([double bond, length as m-dash]Sr3Fe2O5Fe2OS2) and Sr4Fe4O7S2 ([double bond, length as m-dash]Sr4Fe2O6Fe2OS2), designed using a building-block approach, are reported. They are fully charge-ordered with Fe2+ and Fe3+ ions in distinct layers showing independent long-range magnetic order. Complex microstructures in some regions suggest new targets. Mixed-anion compounds are a growth area of solid-state chemistry. Layered structures are often adopted due to anion ordering and desirable properties include tuneable bandgap energies for semiconductors,1 promising thermoelectric properties,2 high-temperature superconductivity3 and complex magnetism.4 A fruitful design method for oxide chalcogenides5 is to use as building blocks individual layers or slabs found in known compounds, and combine them in new ways to target new structures and compositions. We proposed new targets containing the strontium iron oxide slabs from Sr3Fe2O5Cu2S2 or Sr2FeO3CuS6 combined with the iron oxide sulfide layer in Sr2F2Fe2OS2.7 The similar basal lattice parameters of these compounds suggested 1 : 1 intergrowths might form. These targets, conveniently formulated as Sr3Fe2O5Fe2OS2 (compound 1) and Sr4Fe2O6Fe2OS2 (2), were synthesized in high purity from SrO, Fe2O3, Fe, and S by ceramic solid-state synthesis in alumina crucibles within evacuated sealed fused silica tubes heated at 1 °C per minute to 900 °C (enabling sulfur to react before attaining a high vapour pressure) with a dwell time of 48 hours resulting in black powders stable to ambient air. Full synthetic details are in the SI. Structural models were devised by constructing 1 : 1 intergrowths as indicated above, with appropriate interatomic distances, and these accounted well for the powder diffraction patterns of both new products. Both phases contain iron in distinct Fe1 and Fe2 layers and in two different coordination environments: a square pyramidal [FeO5] unit (Fe1—initially assumed to contain Fe3+) and a distorted octahedral [FeO2S4] unit with O atoms arranged trans to one another (Fe2—initially assumed to contain Fe2+). 1 crystallizes in the primitive tetragonal space group P4/mmm with layers of basal-vertex-linked [FeO5] pyramids joined via apical oxide vertices to form double-thickness layers of [FeO5] pyramids (Fig. 1a). 2 (Fig. 1b) crystallizes in the body-centred tetragonal space group I4/mmm with adjacent layers of basal-vertex-linked [FeO5] pyramids separated and shifted by (a + b)/2 in the basal plane, effectively by the insertion of a rock salt layer SrO into the oxide slab present in 1 (Fig. 1c and d). In addition to the different Fe-sites within the phases, there are also different sites occupied by the Sr2+ cations, 12- and 8-coordinate sites in 1 and 9- and 8-coordinate sites in 2 (Fig. S2).
000170200 540__ $$9info:eu-repo/semantics/openAccess$$aby$$uhttps://creativecommons.org/licenses/by/4.0/deed.es
000170200 655_4 $$ainfo:eu-repo/semantics/article$$vinfo:eu-repo/semantics/publishedVersion
000170200 700__ $$aLyon, Annabel R.
000170200 700__ $$aSavvin, Stanislav
000170200 700__ $$aPuente-Orench, Ines
000170200 700__ $$aRahimisheikh, Sepideh
000170200 700__ $$aHadermann, Joke
000170200 700__ $$aGimeno, Magali
000170200 700__ $$aNeidig, Michael L.
000170200 700__ $$aClarke, Simon J.
000170200 773__ $$g62, 18 (2026), 5237-5240$$pChem. commun.$$tChemical Communications$$x1359-7345
000170200 787__ $$tPND data$$tPND data 2/2$$whttps://doi.org/10.5291/ILL-DATA.5-31-2917$$whttps://doi.org/10.5291/ILL-DATA.5-31-3008
000170200 8564_ $$s2492178$$uhttps://zaguan.unizar.es/record/170200/files/texto_completo.pdf$$yVersión publicada
000170200 8564_ $$s2940332$$uhttps://zaguan.unizar.es/record/170200/files/texto_completo.jpg?subformat=icon$$xicon$$yVersión publicada
000170200 909CO $$ooai:zaguan.unizar.es:170200$$particulos$$pdriver
000170200 951__ $$a2026-03-26-14:31:34
000170200 980__ $$aARTICLE