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2005
Iron
I 7100
20- 028
New Orthoferrates of Rubidium and Cesium: α-, β-Cs5[FeIIIO4] and
AI5 [FeIVO4][FeVO4] (AI: Rb, Cs). — The four title compounds are prepared by reaction of stoichiometric mixtures of A metal (A: Rb, Cs), AO2, and Fe2O3 (corundum crucible, argon; 500 °C, 1 h). The new orthoferrates crystallize with new crystal structure
types in the monoclinic space group P21/c with Z = 4 (single crystal XRD). The structures contain isolated FeO4 tetrahedra, which are of nearly ideal tetrahedral geometry
in the two FeIII compounds consistent with the d5 electron configuration of Fe. In contrast, in the mixed valence orthoferrates Cs7[FeO4]2 and Rb7[FeO4]2 the Fe—O distances in the two crystallographically independent FeO4 tetrahedra are in the range of
174—179 pm and thus between those in ferrates(IV) and (V). As a result of the d4 and
d3 electron configuration the FeO4 tetrahedra show significant Jahn-Teller distortion.
— (FRISCH, G.; ROEHR*, C.; Z. Anorg. Allg. Chem. 631 (2005) 2-3, 507-517; Inst.
Anorg. Anal. Chem., Albert-Ludwigs-Univ., D-79104 Freiburg/Br., Germany; Ger.,
Abstr. Eng.) — Schramke
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