Structural properties and FTIR-Raman spectra of the anti-hypertensive clonidine hydrochloride agent and their dimeric species

The structural and vibrational properties of the alpha-adrenergic agonist clonidine hydrochloride agent and their anionic and dimeric species were studied combining the experimental FT-IR and Raman spectra in solid phase with ab-initio calculations based on the density functional theory (DFT). All the calculations were performed by using the hybrid B3LYP with the 6-31G* and 6-311++G** basis sets. The structural properties for those species were studied employing the Natural Bond Orbital (NBO), Atoms in Molecules theory (AIM) and frontier orbitals calculations. The complete assignments of the FTIR and Raman spectra were performed combining the DFT calculations with the Pulay's Scaled Quantum Mechanics Force Field (SQMFF) methodology. Very good concordances between the theoretical and experimental spectra were found. In addition, the force constants for those three species were computed and compared with the values reported for similar antihypertensive agents. The ionic nature of the H -> Cl bond and the high value of the LP(1)N4 -> LP*(1)H18 charge transfer could explain the high reactivity of clonidine hydrochloride in relation to other antihypertensive agent and the strong shifthing of the band assigned to the N-H stretching mode linked to the H-Cl bond toward lower wavenumbers. (C) 2016 Elsevier B.V. All rights reserved.