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Iron stereochemistry in oxygen-containing compounds

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Abstract

The Voronoi-Dirichlet polyhedra (VDP) and the method of intersecting spheres were used to analyze the coordination of 1598 sorts of Fe atoms in the structure of 985 oxygen-containing compounds. The iron atoms whose oxidation number varies from 1 to 6 can coordinate 2 to 8 oxygen atoms in the crystal structure, giving rise to the FeOn coordination polyhedra shaped like square antiprisms (n = 8), octahedra or trigonal prisms (n = 6), square pyramids or trigonal bipyramids (n = 5), tetrahedra or squares (n = 4), triangles (n = 3), or dumbbells (n = 2). The effect of the valence state and the coordination number of iron on the VDP parameters was studied. A general linear correlation between the solid angles of the VDP faces corresponding to Fe-O bonds and the corresponding interatomic distances, which vary over a broad range (1.63–2.77 Å), was established. It is shown in relation to the A2Fe2O5 oxides (A = Ca, Sr) that VDP characteristics make it possible to reveal essential differences in the crystal structures even for isostructural compounds. The FeIVO6 octahedra, unlike isoelectronic MnIIIO6 or CrIIO6 octahedra, display no Jahn-Teller effect. In was shown in relation to CaFeO3 that VDP parameters can be used for the quantitative description of the charge disproportionation in the crystal structure.

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Authors and Affiliations

  1. Samara State University, Samara, Russia

    V. N. Serezhkin, L. B. Serezhkina & D. V. Pushkin

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  1. V. N. Serezhkin
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  2. L. B. Serezhkina
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  3. D. V. Pushkin
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Original Russian Text © V.N. Serezhkin, L.B. Serezhkina, D.V. Pushkin, 2006, published in Koordinatsionnaya Khimiya, 2006, Vol. 32, No. 3, pp. 188–200.

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Serezhkin, V.N., Serezhkina, L.B. & Pushkin, D.V. Iron stereochemistry in oxygen-containing compounds. Russ J Coord Chem 32, 180–191 (2006). https://doi.org/10.1134/S1070328406030043

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