Supramolecular, spectroscopic and computational analysis of weak interactions in some thiosemicarbazones derived from 5-acetylbarbituric acid

• Published in: Journal of molecular structure Vol. 1245; p. 131031
• Main Authors: Castiñeiras, Alfonso, Fernández-Hermida, Nuria, García-Santos, Isabel, Gómez-Rodríguez, Lourdes, Gil, Diego M., Frontera, Antonio
• Format: Journal Article
• Language: English
• Published: Elsevier B.V 05.12.2021
• Subjects: 5-acetylbarbituric acid; Crystal structure; DFT calculations; Heterocycles; Hirshfeld surface; Thiosemicarbazones; Heterocycles; 5-acetylbarbituric acid; Thiosemicarbazones; DFT calculations; Crystal structure; Hirshfeld surface
• ISSN: 0022-2860; 1872-8014
• DOI: 10.1016/j.molstruc.2021.131031

•New thiosemicarbazones derived from 5-acetylbarbituric acid were characterized by XRD.•The crystal packing of compounds is directed by non-covalent interactions.•The Hirshfeld surface analysis was also applied to intermolecular interactions•The energetic features of the assemblies were analyzed using DFT calculations A new series of 5-acetylbarbituric based thiosemicarbazones (TSC) named 5-acetylbarbituric hydrazine-1-carbothioamide (1), N-methyl-(5-acetylbarbituric)hydrazine-1-carbothioamide (2), N-ethyl-(5-acetylbarbituric)hydrazine-1-carbothioamide (3), N,N-dimethyl-(5-acetylbarbituric)hydrazine-1-carbothioamide (4), N'-piperidine-(5-acetylbarbituric)-1-carbothiohydrazide (5) and N'-hexamethyleneimine-(5-acetylbarbituric)-1-carbothiohydrazide (6), has been synthesized from 5-acetylbarbituric acid and N-unsubstituted/substituted thiosemicarbazides. The synthesized compounds were well characterized by elemental analyses, FT-IR, 1H, 13C NMR and mass spectroscopic methods. Three-dimensional molecular structures of three compounds (1⋅DMSO, 2 and 6⋅H2O) were determined by single crystal X-ray crystallography, and an analysis of their supramolecular structure was carried out. The supramolecular features of the X-ray structure were also studied using Hirshfeld surface analysis. Finally, H-bonding networks observed in the solid state X-ray structures of 1⋅DMSO, 2, and 6⋅H2O and unconventional π-stacking dimers in 6⋅H2O were further analyzed by DFT calculations in combination with molecular electrostatic potential surfaces and combined QTAIM/NCIplot computational tools. [Display omitted]