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Kristallstruktur- und Mößbauer-Untersuchungen am Lithiumhexacyanoferrat(III)-Hexamethylentetramin-Addukt Li3[Fe(CN)6] ·2C6H12N4 · 5H20

Pickardt, Joachim; Kähler, Jörg; Rautenberg, Norbert; Riedel, Erwin

FG Anorganische Chemie - Festkörper- und Materialchemie

Crystals of the adduct Li3[Fe(CN)6] · 2C6H12N4-5H2O are orthorhombic, space group I2mm, Z = 2, a = 909.4(5), b = 1046.1(5), c = 1455.8(5) pm. The structure may be regarded as a packing of Fe(CN)6 octahedra and hexamethylenetetramine molecules. The lithium ions are coordinated to nitrogen atoms of both groups and to water molecules. Mossbauer spectra have been recorded for the temperature range between 290 K and 77 K. At all temperatures the spectra show two doublets with nearly identical isomer shifts but different quadrupole splittings, thus indicating the presence of two kinds of hexacyanoferrate(III) ions with slightly different distortions of the ligand spheres around the Fe atoms. The effect is discussed on the assumption of a statistical distribution of one of the lithium ions.