Abstract
The title di-substituted thio-urea, C12H16N2O3S, has the hy-droxy-lethyl and ethyl benzoate substituents bound to the same amine-N atom, and is twisted, having a (+)syn-clinal conformation with the Namine-C-C-O(hydroxyl, carbon-yl) torsion angles of 49.39 (13) and 59.09 (12)°, respectively; the dihedral angle between the almost planar CN2S core and the pendent benzene ring is 69.26 (4)°. In the crystal, supra-molecular layers propagating in the ac plane are formed via a combination of hydroxyl-O-H⋯S(thione), amine-N-H⋯O(hydroxyl, carbon-yl) hydrogen-bonds. The layers stack along the b axis with inter-digitation of the benzene rings allowing the formation of π-π stacking [inter-centroid separation = 3.8722 (7) Å] and parallel C=O⋯π inter-actions. A computational chemistry study shows the conventional hydrogen bonding in the crystal leads to significant electrostatic stabilization but dispersion terms are also apparent, notably through the inter-actions involving the benzene residue.
Highlights
The title di-substituted thiourea, C12H16N2O3S, has the hydroxylethyl and ethyl benzoate substituents bound to the same amine-N atom, and is twisted, having a (+)syn-clinal conformation with the Namine—C—C—O(hydroxyl, carbonyl) torsion angles of 49.39 (13) and 59.09 (12), respectively; the dihedral angle between the almost planar CN2S core and the pendent benzene ring is 69.26 (4)
Supramolecular layers propagating in the ac plane are formed via a combination of hydroxyl-O—HÁ Á ÁS(thione), amine-N—HÁ Á ÁO(hydroxyl, carbonyl) hydrogen-bonds
A computational chemistry study shows the conventional hydrogen bonding in the crystal leads to significant electrostatic stabilization but dispersion terms are apparent, notably through the interactions involving the benzene residue
Summary
The title compound, (I), was characterized crystallographically in a continuation of recent structural studies of tri-substituted thiourea derivatives formulated as (HOCH2CH2)2NC( S)N(H)C( O)C6H4-R-4 for R = Me (Tan, Azizan et al, 2019) and R = NO2 (Tan et al, 2020): these molecules are known for their various applications including biological activity (Saeed et al, 2014). A convenient synthesis for these molecules is via the reaction of NH4(NCS), R2NH and ArC( O)Cl to yield R2NC( S)N(H)C( O)Ar. In an experiment with R = CH2CH2OH and Ar = C6H5, the solution was heated resulting in an apparent rearrangement with deprotonation of one hydroxyethyl group followed by nucleophilic attachment at the carbonyl-C atom along with protonation of the primary amine and cleavage of the original N—C( O) bond to yield (I), formulated as H2NC( S)N(CH2CH2OH)CH2CH2OC( O)C6H5.
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