Synthesis, Crystal Structure, and computational techniques (DFT, HSA, ELF) Studies of a New 2- Ethylanilinium Phosphite[CH3CH2C6H4NH3]PO3

Abstract

Abstract Chemical preparation, crystal structure characterization, and computational techniques (DFT, HAS, and ELF) provided a comprehensive characterization of the structural, electronic, and intermolecular interaction properties for the new synthesized crystal, 2-ethylanilinium phosphite [CH3CH2C6H4NH3]PO3, abbreviated as C8H12NH2PO3.This organic-inorganic phosphite was synthesized by reaction of phosphorous acid H3PO3with a solution of N,N-Dimethylaniline C8H11N. Single crystal X-Ray diffraction analysis shows that this compound crystallizes in the triclinic system with P-1(Z=2)space group, and the unit cell parameters: a=4.6042(2) Å; b=10.3863(4) Å c=10.7848(5) Å, a=90.115(3)°,β=97.878(3)°, g=98.462(3)°, V=505.18(4) Å3. The structure refinement is made by the least-squares method with full matrix at R = 0.036, and wR2 = 0.109 for 1989 independent reflections. In the title structure, anions [H2PO3]- and cations [CH3CH2C6H4NH3]+ are linked together by medium to strong hydrogen bonds, forming a 3D-complex network, which ensures the structural cohesion. A comparative study using standard deviation (SD) among bond lengths and angles, obtained by X-ray diffraction and DFT minimized geometrical descriptors using a B3LYP/lanl2dz/scrf=(solvent=water) /pop=(nbo, savenbos) basis set, which leads to calculate the SD average percentage at (+4.99%) for Bond lengths and at (+2.014%)for Angles. 3D-MEPs and the FMO (HOMO/LUMO) were used to assess the Local and Global reactivity for C8H12NH2PO3. Molecular orbital contributions are evaluated by DOS (Density of States). The intermolecular interactions properties were determined for C8H12NH2PO3 by Hirshfeld surface analyses (HSA). The HSA results indicate that N–H⋯O & O–H⋯O hydrogen bonds are the primary intermolecular interactions responsible for stabilizing the crystal structure of this particular supramolecular assembly. The combined experimental and computational approach allowed a detailed understanding of the synthesized material at the molecular and crystalline level.