2-Chloro- and 2-bromo-3-pyridinecarboxaldehydes: Structures, rotamers, fermi resonance and vibration modes

Abstract

FT-Infrared (4000–400 cm −1) and NIR-FT-Raman (4000–50 cm −1) spectral measurements have been made for 2-chloro- and 2-bromo-3-pyridinecarboxaldehydes. A DFT vibration analysis at B3LYP/6-311++G (d,p) level, valence force-fields and vibrational mode calculations have been performed. Aided by very good agreement between observed and computed vibration spectra, a complete assignment of fundamental vibration modes to the observed absorptions and Raman bands has been proposed. Orientations of the aldehydic group have produced two oblate asymmetric rotamers for each molecule, ON- trans and ON- cis: the ON- trans rotamer being more stable than cis by 3.42 kcal mol −1 for 2-chloro-3-pyridinecarboxaldehyde and 3.68 kcal mol −1 for 2-bromo-3-pyridinecarboxaldehyde. High potential energy barrier ca 14 kcal/mol, induced by steric hindrance, restricts rotamers’ population to ON- trans only. It is observed that, in the presence of bromine, C–H stretching modes are pronounced; a missing characteristic ring mode in chlorine's presence shows at 1557 cm −1; the characteristic ring mode at 1051 cm −1 is diminished; a mixed mode near 707 cm −1 is enhanced. Further, an observed doublet near 1696–1666 cm −1 in both IR and Raman spectra is explained on the basis of Fermi resonance between aldehydic carbonyl stretching at 1696 cm −1 and a combination mode of ring stretch near 1059 cm −1 and deformation vibration, 625 cm −1. A strong Raman aldehydic torsional mode at 62 cm −1 is interpreted to correspond to the dominant ON- trans over cis rotamers population.