Synthesis and crystal structure of some (2,2′-dipyridylamine)(carboxylato)(phenoxo)copper(II) complexes with rather unusual phenoxo ligands

• Published in: Inorganica Chimica Acta 2001-11, Vol.324 (1), p.162-172
• Main Authors: Facchinetti, Alessandro, Marsich, Nazario, Camus, Annamaria, Ugozzoli, Franco, Massera, Chiara, Manotti Lanfredi, Anna Maria
• Format: Article
• Language: English
• Subjects: Axial and equatorial phenolates; Carboxylates; Copper(II) 2,2′-dipyridylamine complexes; X-ray structures
• ISSN: 0020-1693; 1873-3255
• DOI: 10.1016/S0020-1693(01)00571-0

Some ternary Cu(dipyam)(OOCR)(OR) complexes (dipyam=2,2′-dipyridylamine; RCOO −=acetate, benzoate, cmb (2-chloro-5-methylthio-benzoate), mta (methylthioacetate), mtn (2-methylthio-nicotinate); OR −=pnp ( p-nitrophenolate), dcp (2,6-dichlorophenolate), tcp (2,4,6-trichlorophenolate)) have been synthesized. Their IR spectra are included and the X-ray diffraction structure is given for the crystals of [Cu(dipyam)(OOCCH 3)(dcp)] ( I), [Cu(dipyam)(mta)(dcp)] ( II), [Cu(dipyam)(mtn)(dcp)] ( III) and [Cu(dipyam)(cmb)(tcp)] ( IV). The copper coordination is square pyramidal in I, with a rather rare axial position of the phenolate ligand, while in II and III is distorted octahedral with equatorial phenolate and weak apical bonds ( II Cl, S; III Cl, O). The copper coordination in IV can be better described as square planar, but with distortion toward a flattened tetrahedral geometry and with a rather long apical CuO distance, involving an oxygen of the carboxylate ion. The entrance of the phenolate in an axial or equatorial position is due to the geometry imposed to the complex by the auxiliary ligand. Some ternary Cu(dipyam)(OOCR)(OR) complexes (dipyam=2,2′-dipyridylamine; RCOO −=acetate, benzoate, cmb (2-chloro-5-methylthio-benzoate), mta (methylthioacetate), mnt (2-methylthio-nicotinate); OR −=pnp ( p-nitrophenolate), dcp (2,6-dichlorophenolate), tcp (2,4,6-trichlorophenolate)) were synthesized and the four complexes [Cu(dipyam)(OOCCH 3)(dcp)] ( I), [Cu(dipyam)(mta)(dcp)] ( II), [Cu(dipyam)(mnt)(dcp)] ( III) and [Cu(dipyam)(cmb)(tcp)] ( IV) were characterized by X-ray diffraction. The self-assembling of all complexes by NH⋯O hydrogen bonds (in I with cooperative CH⋯Cl interactions) give rise to dimeric units in I, III, IV and to polymeric chains in II.