Zur Struktur der LiMIIMIIIF6-Verbindungen. Neue Verbindungen mit MIII=In und Ti

On the Structure of LiM^IIM^IIIF₆ Compounds. New Compounds with M^III=IN and Ti LiMn^IIInF₆ compounds with M^II = Mg, Mn, Co, Ni, Zn, Cd and Ca crystallize in the Na₂SiF₆ structure. The Ti(III) compound LiMgTiF₆ has trirutile structure, LiMnTiF₆ has Na₂SiF₆ and trirutile structure (H.-T. modification), LiCaTiF₆ and LiCdTiF₆ have Li₂ZrF₆ superstructure. With M^II = Co, Ni and Zn solid solutions trirutile — MF₂(rutile) could be only prepared. The lattice constants of all compounds are reported. For LiMnVF₆ and LiFeGaF₆ too dimorphism Na₂SiF₆ trirutile was observed. In the system LiNiCrF₆ (trirutile) — LiMnCrF₆ (Na₂SiF₆ structure) phase limits of both structures are determined in dependence on the ratio of ionic radii r/r. Magnetic data of the In compounds with M^II = Co and Ni and of the Ti(III) compounds with M^II = Mg, Zn, Mn, just as of α- and β-LiMnVF₆ are also given. The three structures only exist if r reaches from 0.6 to 1.2 Å and r from 0.5 to 0.8 Å. The stability-fields are determined by the ratio of ionic radii r/r_Li, r/r_Li and r/r: trirutile 0.9–1.2, Na₂SiF₆ type 1.2–～1.4 and Li₂ZrF₆ superstructure >1.4. The dependence of rate of ionic radii is explained by the different sharing of MF₆ octahedra.