Vibrational spectra, X‐ray and molecular structure of 1 H ‐ and 3 H ‐imidazo[4,5‐b]pyridine and their methyl derivatives: DFT quantum chemical calculations

Molecular structure, vibrational energy levels and potential energy distribution of 1 H ‐imidazo[4,5‐b]pyridine, 3 H ‐imidazo[4,5‐b]pyridine, 5‐methyl‐1 H ‐imidazo[4,5‐b]pyridine, 6‐methyl‐1 H ‐imidazo[4,5‐b]pyridine and 7‐methyl‐3 H ‐imidazo[4,5‐b]pyridine were determined using density functional theory (DFT) at the B3LYP/6‐31G(d,p) level. The optimised bond lengths and bond angles are in good agreement with the X‐ray data of 5‐methyl‐1 H ‐imidazo[4,5‐b]pyridine obtained in the present work ( Pbca space group; a = 8.660(2), b = 11.078(2), c = 11.078(3) Å, Z = 8). The N + H group plays the role of a proton donor in a medium strong hydrogen bond of the type NH…N, linking the N‐atom of the pyridine with the adjacent molecule related by the symmetry operation: 1/2 − x , y − 1/2, z (N…N = 2.869(25) Å). The presence of hydrogen bond is confirmed by appearance in the IR spectra of a very broad and strong contour in the 2000–3100 cm −1 range. The place of substitution of the methyl group at the pyridine ring influences the proton position of the NH group at the imidazole unit. Copyright © 2007 John Wiley & Sons, Ltd.