Bond-valence parameters of lanthanides

• Published in: Acta crystallographica. Section B, Structural science Structural science, 2006-10, Vol.62 (5), p.745-753
• Main Authors: Trzesowska, Agata, Kruszynski, Rafal, Bartczak, Tadeusz J.
• Format: Article
• Language: English
• Subjects: bond-valence parameters; Chemical bonds; Chemical compounds; Condensed matter: structure, mechanical and thermal properties; Crystalline state (including molecular motions in solids); Exact sciences and technology; lanthanides; Oxidation; Physics; Structure of solids and liquids; crystallography; Theory of crystal structure, crystal symmetry; calculations and modeling
• ISSN: 0108-7681; 2052-5192; 1600-5740; 2052-5206
• DOI: 10.1107/S0108768106016429

Ln—O and Ln—N bond‐valence parameters have been computed in coordination complexes for lanthanides (Ln) at oxidation states other than +3 (CeIV, SmII, EuII and YbII). Moreover, Ln—Cl, Ln—S and Ln—C(π‐bonded) bond‐valence parameters are presented, as calculated for coordination compounds. In general, the bond‐valence parameters decrease in the order Ln—O > Ln—C > Ln—N > Ln—Cl > Ln—S. It has been found that the values of bond‐valence parameters decrease with increasing lanthanide atomic number for coordination compounds. As expected, the values of lanthanide–oxygen and lanthanide–nitrogen bond‐valence parameters diminish with increasing lanthanide oxidation state. Several examples are given where the total valence of the lanthanide ion is apparently incorrectly assigned, as well as cases where bond‐valence method calculations confirm the doubtful oxidation state assignment.