Crystal structure, Hirshfeld surface analysis and computational study of 2-chloro-N-[4-(methylsulfanyl)phenyl]acetamide

Abstract

In the title compound, C9H10ClNOS, the amide functional group –C(=O)NH– adopts a trans conformation with the four atoms nearly coplanar. This conformation promotes the formation of a C(4) hydrogen-bonded chain propagating along the [010] direction. The central part of the molecule, including the six-membered ring, the S and N atoms, is fairly planar (r.m.s. deviation of 0.014). The terminal methyl group and the C(=O)CH2 group are slightly deviating out-of-plane while the terminal Cl atom is almost in-plane. Hirshfeld surface analysis of the title compound suggests that the most significant contacts in the crystal are H...H, H...Cl/Cl...H, H...C/C...H, H...O/O...H and H...S/S...H. π–π interactions between inversion-related molecules also contribute to the crystal packing. DFT calculations have been performed to optimize the structure of the title compound using the CAM-B3LYP functional and the 6–311 G(d,p) basis set. The theoretical absorption spectrum of the title compound was calculated using the TD–DFT method. The analysis of frontier orbitals revealed that the π–π* electronic transition was the major contributor to the absorption peak in the electronic spectrum.

Low-Molecular-Weight Organogelators Based on N-dodecanoyl-L-amino Acids—Energy Frameworks and Supramolecular Synthons

“…Table 1 contains the pairwise interaction energies for the analyzed crystals calculated using the CrystalExplorer at CE-B3LYP/6-31G(d,p) level in kJ/mol. All of the values were scaled by factors 1.057, 0.74, 0.871, and 0.618 for coulombic, polarization, dispersion, and repulsion energy terms, respectively, according to Mackenzie et al [ 37 ].…”

“…For each crystal, a cluster of the closest molecules was generated and the unique pair energies have been calculated using CrystalExplorer [ 56 , 57 , 58 ] with the CE-B3LYP model derived from wavefunctions computed by Gaussian09 [ 59 ]. The energies were scaled by factors 1.057, 0.74, 0.871, and 0.618 for coulombic, polarization, dispersion and repulsion energy terms, respectively, according to Mackenzie et al [ 37 ]. The initial geometry for the calculations was taken from the single crystal diffraction experiments.…”

“…It depends highly on the interactions between the surfactant molecules in terms of the geometry as well as the energetic contributions. Therefore, we decided for the first time to apply the energetic landscapes approach proposed by Mackenzie et al [ 37 ] to explore the gelling abilities of selected low-molecular-weight organogelators (LMOGs)— N -dodecanoyl-L-amino acid derivatives. The energy framework approach was previously successfully applied in explaining many problems regarding polymorphism, co-crystals, supramolecular synthons, solid state reactions and sol-to-gel transition process [ 38 , 39 , 40 , 41 , 42 , 43 , 44 ].…”