Hydrogen bonding in thiobenzamide synthon and its Cadmium complex: Crystal structure and Hirshfeld analysis

• Published in: Journal of chemical sciences (Bangalore, India) India), 2016-09, Vol.128 (9), p.1395-1404
• Main Authors: RIGANE, INES, WALHA, SIWAR, SALAH, ABDELHAMID BEN
• Format: Article
• Language: English
• Subjects: Cadmium sulfide; Chemistry; Chemistry and Materials Science; Chemistry/Food Science; Crystal structure; Hydrogen bonding; Hydrogen bonds; Molecular structure; Octahedrons; Single crystals; Surface area
• ISSN: 0974-3626; 0973-7103
• DOI: 10.1007/s12039-016-1133-x

The thiobenzamid TBA and its Cd(II) complex, dichlorothiobenzamidecadmium(II) [Cd(TBA)Cl 2 ] complex has been synthesized and characterized by FT-IR, FT-Raman and UV–Vis spectroscopy. The crystal and molecular structure of TBA and [Cd(TBA)Cl 2 ] were determined by single crystal X-ray diffraction analysis. The molecular arrangement in the crystal structure of TBA can be described on the basis of supramolecular dimeric synthons built up by four independent TBA molecules stacked via N-H…S hydrogen bonds. The 3D Hirshfeld surfaces and the associated 2D fingerprint plots were investigated for intermolecular interactions. The N-H…S hydrogen bond percentages were estimated to be 23.1%, 22.9%, 30.6% and 27.3% of Hirshfeld surfaces area respectively for each TBA molecule. Synthons are associated through C–H… π interactions at percentage of 33.8%, 38.2%, 24.3% and 19.4% to result in 3D network. The dichlorothiobenzamide cadmium(II) complex bonded by sulfur atom of thiobenzamide shows a double chain of distorted octahedra around the cadmium atoms running along the a axis and the packing is stabilized by intra- and inter-chain hydrogen bonding interactions of the type N–H…Cl and aromatic π … π stacking interactions between ring centroids at 21.8% and 7.6% of the Hirshfeld surface area, respectively. The decomposition of the complex to cadmium sulfide has been investigated by thermogravimetric analysis (TGA). Graphical Abstract Dimeric N-H…S hydrogen bonded thiobenzamid (TBA) synthons, assembled via C-H… π interactions in the solid state, on reaction with cadmium chloride form octahedral double chain complex. The π…π, N-H…Cl and H…H intermolecular interactions dominate the supramolecular self-assembly process.