Effect of Terminal Hydroxy Groups on the Structural Properties of Acyl Thioureas

The 1‐acyl thiourea family [R1C(O)NHC(S)NR2R3] exhibits the flexibility to incorporate a wide variety of substituents into their structure. The structural attributes of these compounds are intricately tied to the type and extent of substitution. In the case of 3‐mono‐substituted thioureas (R2=H), the conformational behavior is predominantly shaped by the presence of an intramolecular N−H ⋅ ⋅ ⋅ O=C hydrogen bond. This study delves into the structural consequences stemming from the inclusion of substituents possessing hydrogen‐donor capabilities within four novel 1‐acyl‐3‐mono‐substituted thiourea derivatives. A comprehensive suite of analytical techniques, encompassing FTIR, Raman spectroscopy, multinuclear (1H and 13C) NMR spectroscopy, single‐crystal X‐ray diffraction, and supported by computational methods, notably NBO (Natural Bond Orbital) population analysis, Hirshfeld analysis, and QTAIM (Quantum Theory of Atoms in Molecules), was harnessed to scrutinize and characterize these compounds. In the crystalline state, these compounds exhibit an intricate interplay of intermolecular interactions, prominently featuring an expansive network of hydrogen bonds between the hydroxy (−OH) groups and the carbonyl and thiocarbonyl bonds within the 1‐acyl thiourea fragment. Notably, the topological analysis underscores significant distinctions in the properties of the acyl thiourea fragment and the intramolecular >C=O ⋅ ⋅ ⋅ H−N bond when transitioning from the isolated molecule to the crystalline environment. The study investigates the structural and electronic properties of four novel 1‐acyl‐3‐mono‐substituted thiourea derivatives. It reveals how intramolecular and intermolecular hydrogen bonding, particularly involving hydroxyl groups, influence the crystal structure. Through extensive spectroscopic and computational analyses, significant changes in electronic distribution and bonding character are observed upon crystallization, offering insights for material science applications.