CRYSTALLOGRAPHIC STUDIES AND STRUCTURAL SYSTEMATICS OF THE C2-C ALKALI-METAL METAVANADATES

Four compounds in the system (Li, Na)VO3 were synthesized and their structures refined in the space group C2 c. Site population analysis showed that their compositions are (Na0.5Li0.5)VO3, (Na0.62Li0.38)VO3, (Na0.71Li0.29)VO3 and (Na0.84Li0.16)VO3. All have the structure of LiVO3 and α-NaVO3 which are related to the C2 c silicate pyroxenes. Structural data of eight compounds in the system (K, Na, Li)VO3 were compiled, and correlations were established by multiple regression analyses between the effective ionic radii rM1 and rM2 of the alkali metal ions and various structural parameters. The size of the M2 site and the relative displacement of the (VO3)∞ chains are found to depend primarily on rM2 only. The size of the M1 site and the amount of chain rotation are affected by both rM1 and rM2. Changes in lattice parameters are related to the chain movements. The anomalous chain configuration of LiVO3 is also discussed. © 1979.