Orientations of water molecule and hydronium ion in 1-methylquinolinium-3-carboxy chloride monohydrate studied by X-ray diffraction, DFT calculations, NMR, FTIR and Raman spectra

• Published in: Journal of molecular structure Vol. 918; no. 1; pp. 39 - 54
• Main Authors: Barczyński, P., Katrusiak, A., Koput, J., Dega-Szafran, Z., Szafran, M.
• Format: Journal Article
• Language: English
• Published: Elsevier B.V 29.01.2009
• Subjects: 1-Methylquinolinium-3-carboxy chloride and its monohydrate; Anions; B3LYP/6-31G(dp) calculations; Chlorides; Diffraction; FTIR; Mathematical models; Molecular structure; Nuclear magnetic resonance; Raman and NMR spectra; X-ray diffraction; X-rays; X-ray diffraction; Raman and NMR spectra; 1-Methylquinolinium-3-carboxy chloride and its monohydrate; FTIR; B3LYP/6-31G(dp) calculations
• ISSN: 0022-2860; 1872-8014
• DOI: 10.1016/j.molstruc.2008.07.022

The structure of 1-methylquinolinium-3-carboxy chloride monohydrate, 3QBWHCl, has been studied by X-ray diffraction, B3LYP/6-31G(d,p) calculations, NMR, FTIR and Raman spectra. The crystals are triclinic, space group P 1 ¯ . The unit cell comprises six symmetry-independent complexes denoted by letters A– F. Each of those 1-methylquinolinium-3-carboxylate is hydrogen-bonded to a water molecule (in four complexes) or a hydronium ion (in two complexes), O–H···O(W) = 2.556–2.585 Å. The water molecules and hydronium ions are hydrogen bonded to two Cl − anions, O(W)–H···Cl − = 3.093–3.119 Å. The Cl − anions and water molecules additionally interact electrostatically with the positively charged nitrogen atom, N +···Cl − = 3.375–3.394 Å, N +···O(W) = 4.027–4.081 Å. Structures of eight most stable complexes ( G– N) have been optimized by the B3LYP/6-31G(d,p) level of theory and the results have been compared with the X-ray data. Linear correlations between the experimental 1H and 13C NMR chemical shifts ( δ exp) of 3QBHCl in D 2O and DMSO- d 6, and the GIAO/B3LYP/6-31G(d,p) calculated magnetic isotropic shielding tensors ( σ calc) using the screening solvation model (COSMO), δ exp = a + bσ calc, are reported. The probable assignments of the anharmonic experimental solid state vibrational frequencies of anhydrous complexes L (3QBHCl and 3QBDCl) based on the calculated B3LYP/6-31G(d,p) harmonic frequencies have been proposed.