Reactions between Cu(II) halide complexes of 2,2′-dipyridylamine and nitrophenolates. X-ray diffraction structure of the [bis(2,2′-dipyridylamine)di( p-nitrophenolato)di(μ-methoxo)dicopper(II)], [Cu(dipyam)(pnp)(μ-OCH 3)] 2, a dimeric complex containing axial phenoxo ligands in square-pyramidal arrangements

• Published in: Inorganica Chimica Acta 2003-06, Vol.349, p.128-134
• Main Authors: Camus, Annamaria, Facchinetti, Alessandro, Marsich, Nazario, Manotti Lanfredi, Anna Maria, Massera, Chiara, Ugozzoli, Franco
• Format: Article
• Language: English
• Subjects: Copper II–2,2′ dipyridylamine complexes; Crystal structures; Phenolate complexes
• ISSN: 0020-1693; 1873-3255
• DOI: 10.1016/S0020-1693(03)00082-3

The reaction between the [Cu(dipyam)Br 2] complex (dipyam=2,2′-dipyridylamine) and nitrophenolates gave products of exchange reactions between halides and phenolates. Starting from [Cu 2(dipyam) 2(OH) 2(H 2O)]Cl 2·2H 2O, o- and p-nitrophenolate complexes with the same rough formula Cu(dipyam)(OR)(OCH 3) (OR= o- or p-nitrophenolate) but a different chemical behaviour have been obtained. The X-ray diffraction analysis shows that the derivative of the p-nitrophenolate is an interesting dimer [Cu(dipyam)(pnp)(μ-OCH 3)] 2 (pnp= p-nitrophenolate), with two centrosymmetrically related five-coordinated copper(II) ions, having a distorted square-pyramidal geometry defined by axial phenolate ligands and by equatorial dipyam nitrogens and μ-methoxo oxygen bridges. The bridging arrangement forms a Cu 2O 2 core, with a Cu⋯Cu separation of 3.062(2) Å. The crystal structures of the [Cu(dipyam)(pnp) 2]·2H 2O and [Cu(dipyam)(onp) 2] complexes (onp= o-nitrophenolate) are also reported. The reaction between the [Cu(dipyam)Br 2] complex and nitrophenolates gave products of exchange reactions between halides and phenolates. Starting from [Cu(dipyam) 2(OH) 2(H 2O)]·2H 2O, o- and p-nitrophenolate complexes with the same rough formula Cu(dipyam)(OR)(OCH 3) but a different chemical behaviour have been obtained. The X-ray crystal structure shows that the p-nitro phenolate derivative is an interesting dimer [Cu(dipyam)(pnp)(μ-OCH 3)] 2 with two centrosymmetrically related five-coordinated copper(II) ions having a distorted square-pyramidal geometry defined by axial phenolate ligands and by equatorial dipyam nitrogens and μ-methoxo oxygen bridges. In the Cu 2O 2, core, the Cu⋯Cu separation is 3.062(2) Å.