Spectral and cyclic voltammetric studies on some intramolecularly hydrogen bonded arylhydrazones: Crystal and molecular structure of 2-(2-(3-nitrophenyl)hydrazono)-5,5-dimethylcyclohexane-1,3-dione

A series of arylhydrazone derivatives (1-7) were prepared by the coupling of acetylacetone/dimedone with respective aromatic diazonium salts and characterized by IR, H-1 and C-13 NMR spectra. The IR and NMR spectral data clearly manifests the effective intramolecular hydrogen bonding in all the cases. Cyclic voltammetric studies certainly indicate that in all the cases the reduced center is C=N bond of hydrazonic moiety. The single crystal X-ray structural analysis of 2-(2-(3-nitrophenyl)hydrazono)-5,5-dimethylcyclohexane-1,3-dione (6) is also reported. Single crystal X-ray analysis of 6 evidences the intramolecular hydrogen bonding with the N(2)center dot center dot center dot C(4) distance of 2.642(15) angstrom, which can be designated as S(6) according to Etter's graph nomenclature. The cyclohexane ring conformation in the molecule (6) can be described as an envelope. RAHB studies suggest that the resonance assistance for hydrogen bonding is significantly reduced for the compound (6) due to the non-planarity of the six atoms which are involved in resonant cycle S(6) of Etter's graph. The planarity of the resonant cycle S(6) is very much disturbed by the conformational requirement of the cyclohexane ring and hence RAHB concept is less operative in this case. (c) 2009 Elsevier B.V. All rights reserved.