Article ID | Journal | Published Year | Pages | File Type |
---|---|---|---|---|
1331383 | Journal of Solid State Chemistry | 2013 | 7 Pages |
The synthesis and characterisation of LaCa2Fe2GaO8 is described. Neutron powder diffraction data reveal LaCa2Fe2GaO8 adopts an anion-vacancy ordered, ‘triple layer’ structure consisting of an OOTLOOTR stacking sequence of layers of (Fe/Ga)O6 octahedra (O) and (Fe/Ga)O4 tetrahedra (T), related to that of the 4-layer brownmillerite structures (a=5.4784(1) Å, b=22.6780(4) Å, c=5.6007(1) Å, space group Pbma). The apex-linked chains of tetrahedra within structure of LaCa2Fe2GaO8 exhibit a cooperative twisting distortion which alternates in direction between adjacent layers of tetrahedra, the first time such an arrangement has been seen in a triple-layer phase. Magnetisation and neutron diffraction data reveal that LaCa2Fe2GaO8 exhibits two magnetic ordering transitions. On cooling below 550 K the phase adopts a state with short range antiferromagnetic coupling within each double layer of (Fe/Ga)O6 octahedra, but only weak coupling between layers. On cooling below 470 K full three-dimensional, G-type antiferromagnetic order is observed.
Graphical abstractLaCa2Fe2GaO8 adopts an anion-vacancy ordered, ‘triple layer’ structure consisting of an OOTLOOTR stacking sequence of layers of FeO6 octahedra (O) and GaO4 tetrahedra (T), in which the chains of apex-linked tetrahedra exhibit a cooperative twisting distortion which alternates in direction between adjacent layers of tetrahedra. On cooling below 550 K, LaCa2Fe2GaO8 adopts a state with strong two-dimensional antiferromagnetic order within each double layer of FeO6 octahedra, but only weak coupling between layers. On cooling below 470 K full three-dimensional antiferromagnetic order is observed.Figure optionsDownload full-size imageDownload as PowerPoint slideHighlights► LaCa2Fe2GaO8 exhibits a novel anion-vacancy ordered triple-layer structure type. ► New structure variant rationalised on the basis of strucutral parameters. ► Multiple magnetic transitions: paramagnetic–two-dimensional–three-dimensional.