Nickel(II) and zinc(II) complexes of N-substituted di(2-picolyl)amine derivatives: Synthetic and structural studies

作者：Goetzke Linda; Gloe Kerstin; Jolliffe Katrina A; Lindoy Leonard F; Heine Axel; Doert Thomas; Jaeger Anne; Gloe Karsten

来源：Polyhedron, 2011, 30(5): 708-714.

DOI：10.1016/j.poly.2010.12.005

• Nickel(II)
• Zinc(II)
• Polypyridyl
• X-ray structure
• Di(2-picolyl)amine

The interaction of di(2-picolyl)amine (1) and its secondary N-substituted derivatives, N-(4-pyridylmethyl)-di(2-picolyl)amine (2), N-(4-carboxymethyl-benzyl)-di(2-picolyl)amine (3), N-(4-carboxybenzyl)-di(2-picolyl)amine (4), N-(1-naphthylmethyl)-di(2-picolyl)amine (5), N-(9-anthracenylmethyl)-di(2-picolyl)amine (6), 1,4-bis[di(2-picolyl)aminomethyl]benzene (7), 1,3-bis[di(2-picolyl)aminomethyl]benzene (8) and 2,4,6-tris[di(2-picolyl)amino]triazine (9) with Ni(II) and/or Zn(II) nitrate has resulted in the isolation of [Ni(1)(NO3)(2)], [Ni(2)(NO3)2], [Ni(3)(NO3)(2)], [Ni(4)(NO3)(2)]center dot CH3CN, [Ni(5)(NO3)(2)], [Ni(6)NO3)(2)], [Ni-2(7)(NO3)4], [Ni-2(8)(NO3)(4)], [Ni-3(9)(NO3)(6)]center dot 3H(2)O, [Zn(3)(NO3)(2)]center dot 0.5CH(3)OH, [Zn(5)(NO3)(2)], [Zn(6) (NO3)(2)], [Zn(8)(NO3)(2)] and [Zn-2(9)(NO3)(4)]center dot 0.5H(2)O. X-ray structures of [Ni(4)(NO3)(2)]center dot CH3CN, [Ni(6)(NO3)(2)] and [Zn(5)(NO3)(2)] have been obtained. Both nickel complexes exhibit related distorted octahedral coordination geometries in which 4 and 6 are tridentate and bound meridionally via their respective N-3-donor sets, with the remaining coordination positions in each complex occupied by a monodentate and a bidentate nitrato ligand. For [Ni(4)(NO3)(2)]center dot CH3CN, intramolecular hydrogen bond interactions are present between the carboxylic OH group on one complex and the oxygen of a monodentate nitrate on an adjacent complex such that the complexes are linked in chains which are in turn crosslinked by intermolecular offset pi-pi stacking between pyridyl rings in adjacent chains. In the case of [Ni(6)(NO3)(2)], two weak CH center dot center dot center dot O hydrogen bonds are present between the axial methylene hydrogen atoms on one complex and the oxygen of a monodentate nitrate ligand on a second unit such that four hydrogen bonds link pairs of complexes; in addition, an extensive series of pi-pi stacking interactions link individual complex units throughout the crystal lattice. The X-ray structure of [Zn(5)(NO3)(2)] shows that the metal centre once again has a distorted six-coordinated geometry, with the N-3-donor set of N-(1-naphthylmethyl)-di(2-picolyl)amine (5) coordinating in a meridional fashion and the remaining coordination positions occupied by a monodentate and a bidentate nitrato ligand. The crystal lattice is stabilized by weak intermolecular interactions between oxygens on the bound nitrato ligands and aromatic CH hydrogens on adjacent complexes; intermolecular pi-pi stacking between aromatic rings is also present.

• 出版日期2011-3-24