Collect. Czech. Chem. Commun. 1999, 64, 600-612

Complexes with New Chelate Anionic Ligands Formed by Nucleophilic Addition in Copper(II) Coordination Sphere. III. The Crystal Structures of (2,2'-Bipyridine-N,N')(cyanato-N)[methyl(2-cyano-2-imidoxy Ethaneimidate-N,N')]copper(II) and (2,2'-Bipyridine-N,N')(2-cyano-2-imidoxy Ethaneimidate-N,N')copper(II)

Michal Dunaj-Jurčoa,*, Ivan Potočňáka, Dušan Mikloša and Robert Klementb

a Department of Inorganic Chemistry, Slovak Technical University, 812 37 Bratislava, Slovakia
b Department of Physical Chemistry, Slovak Technical University, 812 37 Bratislava, Slovakia


Crystal structures of Cu(II) compounds with new chelate anionic ligands are presented. The formulae of these compounds are [Cu(bipy)(mcoe)(NCO)] (1) and [Cu(bipy)(coe)] (2), where bipy is 2,2'-bipyridine, mcoe and coe are the anionic chelate ligands methyl(2-cyano-2-imidoxy ethaneimidate), [(ON)(NC)C-C(NH)(OCH3)]1- (3), and 2-cyano-2-imidoxy ethaneimidate, [(ON)(NC)C-C(NH)(O)]2- (4), respectively, formed by nucleophilic addition of methanol and hydroxide ion to the coordinatively activated β-carbon of the nitroso-dicyanomethanide. Formation of the hydroxide ion from water in the reaction mixture can be explained by protonation of the C(CN)3- anion. The coordination polyhedra in 1 and 2 are quite different. The coordination polyhedron around the Cu(II) ion in 1 is a distorted trigonal bipyramid and in 2 a distorted square. The Cu(II) ion in 1 is coordinated by four N atoms from two bidentate ligands and one N atom from the NCO- group. The crystal structure consists of discrete molecules with {CuN5} chromophore. On the other hand, the Cu(II) ion in 2 is coordinated by four N atoms from two bidentate ligands in square coordination and the molecules are linked by weaker contacts between copper and oxygen atoms (Cu-O1i = 2.503(3), Cu-O2ii = 2.801(3) Å; i = -x, -y, -z + 1; ii = -x + 1, -y, -z + 1) to infinite chains parallel with c. Thus the coordination polyhedron is completed to an elongated tetragonal bipyramid with the {CuN4O*O*} chromophore. The angle O1i-Cu-O2ii is 167.9(1)° and the crystal structure cannot be considered as molecular but consisting of chains running in one direction. Inspection of the bond distances in mcoe and coe indicates strongly delocalized π-bonding systems. This is also supported by the fact that the anions are almost planar with bond angles close to 120°. The calculated Wiberg (bond-order) indices show that due to conjugation, the bonds within the metallocycle in mcoe and coe exhibit partially multiple character.

Keywords: Crystal structure determination; Nucleophilic addition; Coordinative activation; Pseudohalogenides; ESR spectroscopy; Copper; Bipyridine complexes; Chelates.