Quantum-chemical study of the structure of copper(I) acetate and trifluoroacetate oligomers

• Published in: Journal of structural chemistry 2008-09, Vol.49 (5), p.810-817
• Main Authors: Bazhanova, Z. G., Tarasov, Yu. I., Kovtun, D. M., Boltalin, A. I., Novosadov, B. K., Kochikov, I. V.
• Format: Article
• Language: English
• Subjects: Atomic; Atomic/Molecular Structure and Spectra; Chemistry; Chemistry and Materials Science; Inorganic Chemistry; Molecular; Optical and Plasma Physics; Physical Chemistry; Solid State Physics
• ISSN: 0022-4766; 1573-8779
• DOI: 10.1007/s10947-008-0143-z

The results of B3LYP quantum-chemical calculations of the equilibrium structures of [(CX 3 COOCu) 2 ] 3 , [(CX 3 COOCu) 2 ] 2 , and (CX 3 COOCu) 2 oligomers (X = H, F) using the cc-pVTZ correlation-consistent basis for C, O, and F atoms and the Stuttgart 1997 RSC basis and relativistic effective core potential for Cu(I) atoms are presented. The differences in the structures of the free dimer and dimer units in oligomers were studied. The hexamer structure was chosen as the model of a fragment of the crystalline phase. Good agreement was obtained between the experimental and calculated differences between the geometrical parameters of the structures in the “gas phase-crystal” and “acetate-trifluoroacetate” series. Based on the calculated data, the increase in the Cu(I)-Cu(I) bond length in the silver acetate crystal compared with the gas phase can be explained by the effect of the neighboring dimer units of the polymer ribbon, while the increase in the Cu(I)-Cu(I) bond length in gaseous trifluoroacetate compared with acetate, by the acceptor effect of fluorine atoms.