Concomitant polymorphism of a pyridine-2,6-dicarboxamide derivative in a single space group: experimental and molecular modeling study

Spectrochim Acta A Mol Biomol Spectrosc. 2012 Feb;86:614-24. doi: 10.1016/j.saa.2011.11.026. Epub 2011 Nov 20.

Abstract

The title compound, N(2),N(6)-bis{2-[(Z)-2-hydroxybenzylideneamino]phenyl}pyridine-2,6-dicarboxamide (3), has been synthesized by the reaction of 2-{(2-aminophenylimino)methyl}phenol (1) with pyridine-2,6-dicarbonyl dichloride (2), and characterized by elemental analysis, FT-IR and NMR spectroscopies and thermal analysis. Compounds 1 and 3 were evaluated for their antibacterial activities against Gram-positive and Gram-negative bacteria. The catalytic activity of 3 was also studied, and as a result, the in situ prepared three component system Ru(II)/3/KOH is shown to be an efficient catalyst for the transfer hydrogenation reaction of various ketones under mild conditions. Compound 3 has been crystallized in two polymorphic forms under the same conditions, and their crystal structures have been determined using single crystal X-ray diffraction technique. The molecular geometry, vibrational frequencies and gauge-independent atomic orbital (GIAO) (1)H and (13)C NMR chemical shift values of 3 in the ground state have been calculated using the density functional theory (DFT/B3LYP) method with the 6-31G(d) basis set, and compared with the experimental data. The results are in good agreement with experimental data. The effect of different solvents on the geometry, vibrational frequencies, total energies and dipole moments was also studied using the same method by applying the Onsager Model. There are subtle differences in the conformations and packing of the two polymorphs as a consequence of intermolecular hydrogen bonding interactions. Therefore, DFT calculations for the hydrogen bond interactions in the polymorphs were carried out using same basis set. The changes of thermodynamic properties from the monomers to 3 with the temperature ranging from 200 K to 400 K have been obtained using the statistical thermodynamic method.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Anti-Bacterial Agents / chemistry
  • Anti-Bacterial Agents / pharmacology
  • Catalysis
  • Crystallography, X-Ray
  • Electricity
  • Entropy
  • Hydrogen Bonding
  • Magnetic Resonance Spectroscopy
  • Models, Molecular*
  • Molecular Conformation
  • Nonlinear Dynamics
  • Pyridines / chemical synthesis
  • Pyridines / chemistry*
  • Quantum Theory
  • Spectroscopy, Fourier Transform Infrared
  • Surface Properties
  • Temperature
  • Vibration

Substances

  • Anti-Bacterial Agents
  • Pyridines
  • pyridine-2,6-dicarboxamide