Conformational studies of mixed-ligand copper(II) chelates. Crystal and molecular structure of ( N, N-dimethyl- N′-ethyl-1,2-diaminoethane-(1-phenyl-1,3,-butanedionato)copper(II) perchlorate

Abstract

The IR and ligand field spectra and the structure of the mixed-ligand compound [ N, N-dimethyl- N′-ethyl-1,2-diaminoethane(1-phenyl-1,3-butanedionato)(perchlorato)copper(II)]), [Cu(dmeen)bzac(OClO 3)], are reported. The structure was determined by single crystal X-ray diffraction analysis (triclinic, space group P 1, a = 8.581(6), b = 9.669(6), c = 12.664(6) A ̊ , α = 103.32(6), β = 103.33(6), γ = 91.43(6)°, Z = 2, R = 0.0628, R w = 0.1607 ). The structure is square pyramidal with the apical position occupied by one oxygen of the tetrahedral perchlorato group (distance from copper 2.452(5) Å). The plane of the phenyl ring is tilted forming an angle of 16.72(14)° with the plane of the β-dionato moiety. The nitrogenous base adopts the gauche conformation with torsional angle of 108.72(14)°. The ethyl group is cis oriented relative to the phenyl group, occupying the equatorial position with the vector of the carbon-nitrogen bond forming an angle of 143.9(3)° with the CuNN plane. The interactions of the adjacent axial hydrogen with an oxygen of the perchlorato group result in hydrogen bond formation. The IR spectra reveal that in the solid state the Br − or Cl − displace easily the ClO 4 − group. The shifts in the ligand field spectra indicate that polar solvents participate in donor-acceptor interactions with the metal centre along an axis perpendicular to the CuN 2O 2 plane.