Single-Crystal Investigation, Hirshfeld Surface Analysis, and DFT Study of Third-Order NLO Properties of Unsymmetrical Acyl Thiourea Derivatives

Abstract

In the current research work, unsymmetrical acyl thiourea derivatives, 4-((3-benzoylthioureido)­methyl)­cyclohexane-1-carboxylic acid (BTCC) and methyl 2-(3-benzoylthioureido)­benzoate (MBTB), have been synthesized efficiently. The structures of these crystalline thioureas were unambiguously confirmed by single-crystal diffractional analysis. The crystallographic investigation showed that the molecular configuration of both compounds is stabilized by intramolecular N–H···O bonding. The crystal packing of BTCC is stabilized by strong N–H···O bonding and comparatively weak O–H···S, C–H···O, C–H···π, and C–O···π interactions, whereas strong N–H···O bonding and comparatively weak C–H···O, C–H···S, and C–H···π interactions are responsible for the crystal packing of MBTB. The noncovalent interactions that are responsible for the crystal packing are explored by the Hirshfeld surface analysis for both compounds. The void analysis is performed to find the quantitative strength of crystal packing in both compounds. Additionally, state-of-the-art applied quantum chemical techniques are used to further explore the structure–property relationship in the above-entitled molecules. The optimization of molecular geometries showed a reasonably good correlation with their respective experimental structures. Third-order nonlinear optical (NLO) polarizability calculations were performed to see the advanced functional application of entitled compounds as efficient NLO materials. The average static γ amplitudes are found to be 27.30 × 10–36 and 102.91 × 10–36 esu for the compounds BTCC and MBTB, respectively. The γ amplitude of MBTB is calculated to be 3.77 times larger, which is probably due to better charge-transfer characteristics in MBTB. The quantum chemical analysis in the form of 3-D plots was also performed for their frontier molecular orbitals and molecular electrostatic potentials for understanding charge-transfer characteristics. We believe that the current investigation will not only report the new BTCC and MBTB compounds but also evoke the interest of the materials science community in their potential use in NLO applications.

Synthesis, Spectroscopic Characterization, Single-Crystal Structure, Hirshfeld Surface Analysis, and Antimicrobial Studies of 3-Acetoxy-2-methylbenzoic Anhydride

“…The Hirshfeld surface was analyzed with CrystalExplorer21 to identify various intermolecular contacts in the crystal structure. − The analysis of the 3D Hirshfeld surface (HS) and 2D fingerprint plots (FPs) were performed in order to describe the molecular structure of AMA. The surfaces mapped over d norm , shape index, and curvedness were shown in Figure .…”

Third-order optical nonlinearities of zinc porphyrins accommodated in the cavity of a doughnut-like molybdenum crown cluster

“…54 In addition, the order of γ values of hybrids 1-3 is as follows: hybrid 1 > hybrid 2 > hybrid 3, which may be related to the fact that the -COOH of ZnTCPP has -CvO and -OH, having more chances to form hydrogen bonds with the H 2 O, μ 3 -OH and a large number of μ 2 -O ligands of {Mo 176 } than with the -OH of ZnTHPP and the -NH 2 of ZnTAPP. 55 As shown in Table S1, † the β value of hybrid 1 is higher than those of other NLO materials reported in the literature, indicating that hybrid 1 has an excellent NLO response.…”

Synthesis, crystal structure and Hirshfeld surface analysis of aqua(3-methoxycinnamato-κO)bis(1,10-phenanthroline-κ2 N,N′)cobalt(II) nitrate

“…The two-dimensional fingerprint plots provide quantitative information about the non-covalent interactions and the crystal packing in terms of the percentage contribution of the interatomic contacts (Spackman & McKinnon, 2002;Ashfaq et al, 2021) Co(C 10 H 9 O 3 )(C 12 H 8 N 2 ) 2 (H 2 O)]NO 3 3 of 5 Figure 3 Crystal packing of the title compound showing the layers parallel to the bc plane formed by thestacking interactions between the pyridyl rings of the 1,10-phenanthroline units (blue and cyan). Hydrogen bonds are shown by dashed cyan lines.…”

“…is illustrated in Fig. 4 using colours to indicate contacts that are shorter (red areas), equal to (white areas), or longer than (blue areas) the sum of the van der Waals radii (Ashfaq et al, 2021). The red spots on the surface mapped over d norm (Fig.…”