Synthesis, single crystal X-ray structure determination, Hirshfeld surface evaluation, void analysis, interaction energies, energy frameworks and density functional theory studies of 1-(4-methylbenzoyl)thiourea

The current research work successfully presents facile synthesis, single crystal X-ray structure determination, Hirshfeld surface (HS) analysis, and Density functional theory (DFT) studies of 1-(4-methylbenzoyl)thiourea. Accordingly, the synthesized compound crystallized in triclinic P -1 space group with a = 7.3464 (5) Å, b = 8.2696 (5) Å, c = 8.5337 (5) Å, α = 88.349 (5)°, β = 72.206 (5)°, γ = 69.901 (6)°, Z = 2 and V = 461.89 (5) ų. In the crystal structure, the molecules are linked through intermolecular N—H···O, C—H···O, C—H···S and N—H···S bifurcated hydrogen bonds, enclosing R₂²(8), R₂²(14) and R₄⁴(11) ring motifs, into 2D network. HS analysis explored weak intermolecular interactions and indicated significant contributions responsible for crystal packing are H…H (41.0%), H…S/S…H (21.6%), H…C/C…H (12.7%) and H…O/O…H (9.9%) interactions, where hydrogen bonding and van der Waals contacts were dominant. Crystal voids analysis confirmed the absence of any large cavity within the packed crystal, suggesting higher mechanical stability of the crystal. Furthermore, analysıs of the electrostatic, dispersion and total energy frameworks augmented stabilization through electrostatic energy contribution. Moreover, optimized molecular structure, using DFT at B3LYP/6–311G(d,p) level was compared with the experimentally determined one. HOMO–LUMO energy gaps were determined and the molecular electrostatic potential (MESP) surfaces are calculated at B3LYP/6–31 G level to predict possible sites for electrophilic and nucleophilic attacks. DFT computations, through stable terminal HOMO and whole molecule LUMO spread, and significant polarity predicted amphoteric behavior of the synthesized 1-(4-methylbenzoyl)thiourea for its reaction with an electrophile or nucleophile.