Crystal and molecular structure and ESR spectra of a dimeric dialkoxo-bridged five-coordinate copper(II) complex

The crystal and molecular structure of bis(N,N-bis(2-(diethylamino)ethyl)-2-hydroxyethylamino-O)dicopper(II) diperchlorate has been determined by X-ray diffractometry data. The crystals are monoclinic, of space group P2 1/n, with cell dimensions a = 9.349 (2) Å, b = 17.676 (4) Å, c = 11.720 (3) Å, and β = 93.02 (2)°. The structure was solved by three-dimensional Patterson and Fourier syntheses and refined by least-squares techniques to a final conventional R factor of 0.055 over the 1367 independent observed reflections. The structure consists of dinuclear [Cu 2(bdhe) 2] 2+ cations, which possess a center of symmetry, and of perchlorate anions. The copper(II) ions achieve five-coordination by sharing the oxygen atoms of the ligand. The arrangement of the ligands around the metal ion is intermediate between a trigonal-bipyramidal and a square-pyramidal model. The copper(II)-copper(II) distance is 3.044 (2) Å. Single-crystal ESR spectra of the zinc(II)-doped complex were recorded in order to relate the structural data to the electronic properties. The anisotropic g values and their principal directions were reproduced through an angular overlap (AO) model. The magnetic susceptibility data are discussed within the same formalism. © 1980 American Chemical Society.