Spectres de Vibration et Transition de Phase des Complexes Formés Entre l'Acide Oxalique et la Pyridine

Raman and infrared spectra (4000–20 cm−1) of polycrystalline pyridine–oxalic acid complexes were investigated between 80 and 300 K and an assignment in term of group frequencies is given. The 2:2 and 2:3 compounds are spectroscopically identified and the OH…O and NH…O hydrogen bonds characterized. The spectroscopic results are consistent with crystallographic data. With the deuterated oxalic acid, only one 1:1 complex is obtained and its crystalline structure is different. From spectroscopic analysis, it is found to be built of infinite chains of hydrogenoxalate ions with strong OD…O hydrogen bonds (νOD about 1300 cm−1 and estimated Ro…o = 2.53 A). The pyridinium moiety (C5H5ND+) forms ND…O hydrogen bonds characterized by a νND frequency of 2130 cm−1 and an N…O distance of 2.75 A. Further, in this compound, one second-order phase transition is observed at 235 K and the structural modifications are discussed.

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