The crystal and magnetic structures of LaCa(2)Fe(3)O(8) and NdCa(2)Fe(3)O(8).

The crystal and magnetic structures of LaCa(2)Fe(3)O(8) and NdCa(2)Fe(3)O(8) have been established using a combination of x-ray, neutron and electron diffraction. It was already considered likely that LaCa(2)Fe(3)O(8) and NdCa(2)Fe(3)O(8) were made up of stacked perovskite-like layers of FeO(6) octahedra, with every third layer being replaced by a layer of tetrahedrally coordinated Fe, rather like a variation on the Brownmillerite (Ca(2)Fe(2)O(5)) structure type. We have gone further and determined a likely space group for this Grenier phase and determined the magnetic structure of the compounds at room temperature. The space group is found to be P 2(1)ma (b axis as the long axis), and the crystal structure has been refined, subject to the stacking faulting along the long axis that is apparent in electron diffraction patterns. The magnetic structure of LaCa(2)Fe(3)O(8) is shown to consist of antiferromagnetically ordered Fe(3+) ions on a collinear G-type antiferromagnetic structure, with the magnetic moments most likely (anti)parallel with the c axis, and of magnitude 3.4 ± 0.2μ(B) (3.6 ± 0.2μ(B) for NdCa(2)Fe(3)O(8)). The result is reasonable given the magnetic structures of the end members of the La(1-x)Ca(x)FeO(3) series, LaFeO(3) (x = 0) and Ca(2)Fe(2)O(5) (x = 1).