X-ray and DFT studies of the structure, vibrational and NMR spectra of 2-amino-pyridine betaine hydrochloride

• Published in: Journal of molecular structure Vol. 744; pp. 59 - 73
• Main Authors: Szafran, M., Kowalczyk, I., Koput, J., Katrusiak, A.
• Format: Journal Article
• Language: English
• Published: Elsevier B.V 03.06.2005
• ISSN: 0022-2860; 1872-8014
• DOI: 10.1016/j.molstruc.2004.11.087

The effect of hydrogen bonding, inter- and intramolecular electrostatic interactions on the conformation of 2-amino-pyridine betaine hydrochloride (1-carboxymethyl-2-amino-pyridinium chloride), 2-NH 2PBH⋯Cl(c), in the crystal and its isolated molecules has been studied by X-ray diffraction, FT-IR, Raman, 1H and 13C NMR spectroscopies, and by DFT calculations. In the crystal, the Cl − anion is connected with protonated betaine via hydrogen bond, O–H⋯Cl −= 2.975(2) Å, two N(12)–H⋯Cl − hydrogen bonds and two N(1) H⋯Cl − intermolecular electrostatic interactions. Two minima are located in the potential energy surface at the B3LYP/6-31G(d,p) level, 2-NH 2PBH⋯Cl(t) and 2-NH 2PB⋯HCl(c), with the latter being 20,7 kcal/mol higher in energy. The optimized bond lengths and angles of 2-NH 2PBH⋯Cl(t) at B3LYP level of theory are in good agreement with X-ray data, except for the conformation of the COOH group, which is cis ( syn) in the crystal and trans ( anti) in the single molecule. The probable assignments for the anharmonic experimental solid state vibrational spectra of 2-NH 2PBH⋯Cl(c) and 2-ND 2PBD⋯Cl(c) based on the calculated B3LYP/6-31G(d,p) harmonic frequencies have been made. 1H and 13C NMR screening constants for both single molecules have been calculated in the GIAO/B3LYP/6-31G(d,p) approach. Linear correlation between the calculated and experimental 1H chemical shifts holds only for cis conformer. The lack of such a correlation for trans conformer indicates that it is absent in D 2O solution.