, Volume 60, Issue 10, pp 2124-2127
Date: 26 Jun 2012

Synthesis and molecular structure of the cobalt(ii) chloride complex with bis(α-pyridyl)-substituted bispidinoaza-14-crown-4

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Abstract

The reaction of cobalt(ii) chloride with bis(benzo)bispidinoaza-14-crown-4 (L) containing two α-pyridyl substituents affords complex [Co(L)(H2O)][CoCl4] (1). The structure of complex 1 was determined by X-ray diffraction analysis. In structure 1, molecule L is coordinated to the neutral Co(1) atoms as an N, N, N, N-tetradentate-chelating ligand. The tetrachlorocobaltate dianion acts as a counterion. The coordination polyhedron of the Co atom in complex 1 is an octahedron, and that of the Co(2) atom in the anion is a tetrahedron. The coordination polyhedra of the Co atoms in complex 1 are linked by the bridging chlorine atom. In the octahedron of the Co(1) atom, two five-membered and two six-membered nonplanar chelate metallocycles, which are conjugated with each other along the Co(1)-N(1) and Co(1)-N(2) bonds, undergo ring closure. All bond lengths of the Co(1) atom with the N atoms range from 2.098(4) to 2.228(5) Å, and the Co(2)-Cl bond lengths change from 2.233(2) to 2.331(2) Å. The longest Co(1)-Cl(4) bond (2.558(2) Å) is that with the metal ion. A molecule of complex 1 is stabilized by strong intramolecular hydrogen bonds involving the crown ether fragment.

Dedicated to Academician of the Russian Academy of Sciences V. N. Charushin on the occasion of his 60th birthday.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 2066–2088, October, 2011.