N-H···S hydrogen bonds in a new family of ion-pair complexes between cationic nickel tetraazabicyclononane and anionic metal dithiolates: synthesis characterization and properties of [Ni(C9H22N6)][M(mnt)2](MII = Cu, Ni, Pd)

Madhu, Vedichi ; Das, Samar K. (2006) N-H···S hydrogen bonds in a new family of ion-pair complexes between cationic nickel tetraazabicyclononane and anionic metal dithiolates: synthesis characterization and properties of [Ni(C9H22N6)][M(mnt)2](MII = Cu, Ni, Pd) European Journal of Inorganic Chemistry, 2006 (7). pp. 1505-1514. ISSN 1434-1948

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Official URL: http://onlinelibrary.wiley.com/doi/10.1002/ejic.20...

Related URL: http://dx.doi.org/10.1002/ejic.200500751

Abstract

The ion-pair complexes [Ni(C9H22N6)][Cu(mnt)2] (1), [Ni(C9H22N6)][Ni(mnt)2] (2), and [Ni(C9H22N6)][Pd(mnt)2] (3; mnt2- = 1,2-dicyanoethylenedithiolate, C9H22N6 = 3,7-bis(2-aminoethyl)-1,3,5,7-tetraazabicyclo[3.3.1]nonane) have been synthesized and characterized by elemental analysis, IR, UV/Vis, and 1H NMR spectroscopy, X-ray powder diffraction, and electrochemical studies, and unambiguously by single-crystal X-ray crystallography. All three complexes are isostructural and crystallize in the monoclinic space group P21/n. The N-H···S-type hydrogen-bonding capabilities of the classical sulfur-containing complex anions [MII(mnt)2]2- (A; M = Cu, Ni and Pd) have been explored using amine groups containing the nickel complex cation [Ni(C9H22N6)]2+ (C) in the ion-pair compounds 1, 2, and 3. In the crystal, the cation interacts with two different anions through three N-H···S hydrogen bonds and, likewise, the anion is hydrogen-bonded to two different cations through three hydrogen bonds, resulting in the formation of a chain-like arrangement. The average N-H···S hydrogen-bond lengths are 3.498(3), 3.505(3), and 3.490(5) Å for compounds 1, 2, and 3, respectively. Another crystallographic feature is the presence of CC-AA-CC-AA-type packing with short S...Ni contacts in the crystal structures. Besides crystallography, the existence of these N-H...S hydrogen bonds between cation [Ni(C9H22N6)]2+ (C) and anion [MII(mnt)2]2- (A) is strongly supported by the IR and 1H NMR studies. The stability of the [Ni(C9H22N6)]2+ (C) moiety in compounds 1, 2, and 3 is discussed in light of electrochemical studies performed on these compounds and [Ni(C9H22N6)](ClO4)2. Complex 1 exhibits a well-resolved ESR signal corresponding to a Cu2+ (d9) system at liquid-nitrogen temperature.

Item Type:Article
Source:Copyright of this article belongs to John Wiley and Sons.
Keywords:Hydrogen Bonds; Ion Pairs; N Ligands; Nickel; S Ligands
ID Code:63408
Deposited On:29 Sep 2011 04:29
Last Modified:29 Sep 2011 04:29

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