Spectroscopic and structural elucidation of 4-dimethylaminopyridine and its hydrogensquarate

A distortion of the aromatic character and stabilization of the imino-form as a result of the protonation of 4-dimethylaminopyridine was established by IR-, UV- and H-1 NMR-spectral analysis of 4-diaminopyridinium hydrogensquarate. Quantum chemical calculations were carried out at MP2 and B3LYP levels of theory and a 6-311++G** basis set with a view to determining the changes in geometrical parameters and IR-spectroscopic characteristics resulting from N-py protonation. Linear-dichroic IR-spectroscopy coupled with the orientation techniques of solid samples as liquid crystal suspensions and melted solid polycrystalline films was applied for the identification of the IR-bands, characteristic for the structural fragments of the neutral and imino-form of the pyridine derivative. The spectral results were compared with the structure, obtained by a single crystal X-ray analysis. The salt contains dimmers of hydrogensquarate anions and N-py protonated cations of which the former are stabilized by strong intermolecular OH. . .O interactions (2.552 angstrom and 143.1(2)degrees). The 4-diaminopyridinium cation interacts with the anion through moderate NH. . .O bonds (2.729 angstrom and 165.0(0)degrees). Individual cations are pi-pi stacked with their neighbors at a distance of 3.406 angstrom. (c) 2008 Elsevier B.V. All rights reserved.