Structural, vibrational and DSC investigations of the bis-4-benzyl piperidinium tetraoxoselenate monohydrate crystal.

A new organic-inorganic salt, bis-4-benzyl piperidinium tetraoxoselenate monohydrate has been synthesized and characterized by X-ray diffraction, FT-IR and FT-Raman spectroscopies. The title compound crystallizes in the monoclinic system P2(1)/c at room temperature with the following parameters: a=8.617(3)Å, b=27.140(9)Å, c=10.926(5)Å, ß=96.46(4)° and Z=4. Its vibrational spectra have been discussed on the basis on quantum chemical density theory (DFT) calculation using B3LYP/6-31G(*) approach. The role of the intermolecular interaction in this crystal is analyzed. Acidic protons of the selenate group were transferred to the organic cation giving the singly-protonated cation. The ability of ions to form spontaneous three-dimensional structure through O-H···O and N-H···O hydrogen bond is fully utilized. These hydrogen bonds give notable vibrational effects.

Vibrational study of phase transition in N-benzyl methyl ammonium dihydrogenmonophosphate monohydrate.

Raman spectra (100-3200 cm(-1)) of polycrystalline samples of C(6)H(5)CH(2)NH(2)CH(3)H(2)PO(4).H(2)O were studied at temperature ranging from 77 to 350 K. By comparison with homologue compounds and calculated wavenumbers, an assignment of the observed bands is proposed. The thermal evolution of Raman spectra reveals an order-disorder phase transition at about 120 K involving the hydrogen bonds coupled with the distortion of the organic cations. The line at 244 cm(-1)assigned to tau(CH(3)) shows a remarkable evolution across the transition. Therefore, a careful analysis of the thermal evolution of this mode was performed using Porto model. The activation energy, obtained from the plot of Deltanu(1/2) versus temperature, is E(a)=1.27 kcal mol(-1). This value is of the same order of magnitude as the one found for homologue hydrogen bonded compounds.