Cyanato-copper(II) complexes with organic ligands—XIII[1]: Isomerism with dicyanato-bis(2,4-Lutidine (cas 108-47-4))-copper(II)

Add time:08/25/2019    Source:sciencedirect.com

Two new isomeric forms of Cu(NCO)2(2,4-lutidine)2, a violet β and a blue γ, were prepared and examined by several physical methods. According to X-ray diffraction patterns the crystal structure of the β-isomer is very close to that of the known α-isomer, whereas the γ-isomer has a considerably different crystal structure. The electronic spectra indicate a tetragonal structure for the β-isomer, this being slightly more distorted than the α-form, and a pseudooctahedral structure for the γ-isomer. The IR spectra give evidence for N-bridging by the NCO groups in the γ-isomer which is ferromagnetic, and the temperature dependence of its susceptibility conforms with an anisotropic Ising model for g = 2·19 and 2J = +9·0 cm−1. In this isomer axial ligation of Cu(NCO)2(2,4-lutidine)2 entities takes place by nitrogen atoms from the NCO groups. These results show that α- and β-Cu(NCO)2(2,4-lutidine)2 represent pure distortion isomers, and that the reduced distortion of γ-Cu(NCO)2(2,4-lutidine)2, by comparison with the α- and β-form, is related to the linkage isomerism.

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