Synthesis and characterization of p -xylylenediaminium bis(nitrate). Effects of the coordination modes of nitrate groups on their structural and vibrational properties

Abstract

The p-xylylenediaminium bis(nitrate) compound have been synthesized and then, it was characterized by using Fourier Transform infrared (FT-IR) in the solid phase and, by using the Ultraviolet-Visible (UV-Visible) and Hydrogen and Carbon Nuclear Magnetic Resonance (1 Hand 13 C-NMR) spectra in aqueous solution and in dimethylsulfoxide solvent. In this work, two monodentate and bidentate coordination modes were considered for the nitrate ligands in both media in order to study the structural and vibrational properties of that salt. Hence, the natural bond orbital (NBO), atoms in molecules (AIM), Merz-Kollman (MK) charges, molecular electrostatic potentials (MEP) and frontier orbitals studies were performed for p-xylylenediaminium bis(nitrate) and their cation and anion species taking into account for the salt those two coordination modes for the nitrate ligands. The intermolecular interactions of this salt were also evaluated by Hirshfeld surface analysis. The B3LYP calculations performed by using the hybrid method and the 6-311G* and 6-311++G** basis sets generate monodentate and bidentate structures with C i and C 2 symmetries, respectively. The force fields and the force constants values for these two structures were also computed and their complete vibrational assignments were performed by using those both levels of theory. The strong band at 1536 cm-1 , the bands between 2754 and 2547 cm-1 and the bands between 1779 and 1704 cm-1 support clearly the presence of the dimeric species while the IR bands at 1986/1856 cm-1 could justify the presence of the bidentate species in the solid phase.

A proton transfer compound template phenylethylamine: Synthesis, a collective experimental and theoretical investigations

“…2b). The interatomic ( ) ( ) distances and the bonding angles of (NO 3 -) collected in Table 3 do not show any particularity compared to those generally encountered in nitrates known until now [29,30]. Concerning the organic cation, the geometric characteristics classified in Table 3 are comparable to those observed for the same cation crystallizing with other types of anions [31].…”

DFT study of species derived from the narcotic antagonist naloxone

“…The natures of the reached stationary points for those three structures were checked with the vibrational frequencies. The atomic charges, molecular electrostatic potentials, bond orders and topological properties were obtained with the versions 3.2 of NBO and AIM2000 programs [44,45] while the frontier orbitals and some descriptors [31][32][33][34][35][36][37][38][39][40] were used to predict kinetics stabilities, reactivities and behaviours in both media. Vibrational analyses for the three species of naloxone were performed computing the harmonic force fields with the scaled mechanical force field (SQMFF) methodology and the version 7.0 of Molvib program [27][28][29] by using the normal internal coordinates and transferable scaling factors.…”

“…Reactivities of different species are predicted by using the gap values calculated from the molecular frontier orbitals, as suggested by Paar and Pearson [31] while the predictions of its behaviours are performed with some important descriptors by using equations recommended in the literature [32][33][34][35][36][37][38][39][40]. Here, the HOMO, LUMO and energy band gaps for the three species of naloxone in both media were calculated with the B3LYP/6-31G* method and the results are presented in Table 9.…”

“…Here, the HOMO, LUMO and energy band gaps for the three species of naloxone in both media were calculated with the B3LYP/6-31G* method and the results are presented in Table 9. In the same Table are summarized the chemical potential (μ), electronegativity (χ), global hardness (η), global softness (S), global electrophilicity index (ω) and global nucleophilicity index (E) descriptors [32][33][34][35][36][37][38][39][40]. Note that the equations used to calculate the descriptors are also presented in that table.…”

“…Besides, the scaled quantum mechanical force field (SQMFF) method and the Molvib program [27][28][29] were employed to perform the complete vibrational assignments of its experimental available infrared, attenuated total reflectance (ATR) and Raman spectra [30]. Reactivities and behaviours of three species of naloxone were also predicted by using the frontier orbitals and equations available from the literature [31][32][33][34][35][36][37][38][39][40]. The predicted properties for naloxone in both media were compared with those published for other alkaloids [1][2][3][4][5][6][7].…”