期刊
INORGANICA CHIMICA ACTA
卷 358, 期 6, 页码 1918-1926出版社
ELSEVIER SCIENCE SA
DOI: 10.1016/j.ica.2004.12.056
关键词
thiodiacetic acid; thiodiglycolic acid; copper(II) complex; imidazole; 5-methyl-phenanthroline; crystal structure; ligand conformation
Three new thiodiacetato-Cu(II) chelates have been synthesized and studied by X-ray crystallography and by thermal, spectral and magnetic methods. [Cu(tda)](n) (1) is a 3D-polymer with a pentadentate tda, which acts with afac-O-2 + S(apical)-tridentate chelating conformation and as a twofold anti, syn-mu-eta(1):eta(1) carboxylate bridge. In its square pyramidal Cu(II) coordination (type 4 + 1) four O(carboxylate) donors define a close regular square base, but the Cu S(apical) bond deviates 27.4 degrees from the perpendicular to the mean basal plane. Each anti,syn-bridging carboxylate group exhibits two C-O (average 1.26(1) angstrom) and two Cu-O bonds (average 1.958(7) angstrom), which are very similar in length to each other. In contrast, the mixed-ligand complexes of [Cu(tda) (Him)(2)(H2O)] (compound 2, distorted octahedral, type 4 + 1 + 1) and [Cu(tda)(5Mphen)] center dot 2H(2)O (compound 3, distorted square pyramidal, type 4 + 1) have molecular structures and the tda ligand displays only a fac-O-2, + S(apical)-tridentate conformation. The Cu-S(apical) bond lengths (2.570(1), 2.623(1) or 2.573(1) angstrom for 1, 2 or 3, respectively) are shorter than those previously reported for closely related Cu(II)-tda derivatives. The different tda ligand roles in their Cu(II) derivatives are rationalized on the basis of crystal packing forces driving in the absence or presence of auxiliary ligands (with two or three N-donor atoms). (c) 2005 Elsevier B.V. All rights reserved.
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