Crystal structure, Hirshfeld surface analysis, and DFT studies of N-(2-chlorophenylcarbamothioyl)cyclohexanecarboxamide

Abstract

N-(2-Chlorophenylcarbamothioyl)cyclohexanecarboxamide was characterized by a single crystal X-ray diffraction study. Crystal data for this compound, C₁₄H₁₇ClN₂OS; Monoclinic, space group P2₁/n with Z = 4, a = 5.2385(10) Å, b = 17.902(4) Å, c = 15.021(3) Å, β = 90.86(3)°, V = 1408.5(5) Å³, T = 153(2) K, μ(MoKα) = 0.413 mm^-1, Dcalc = 1.400 g/cm³, 9840 reflections measured (7.082° ≤ 2Θ ≤ 50.378°), 2519 unique (R_int = 0.0406, R_sigma = 0.0335) which were used in all calculations. The final R₁ was 0.0397 (I > 2σ(I)) and wR₂ was 0.0887 (all data). The puckering parameters (q₂ = 0.019(3) Å, q₃ = 0.578(3) Å, θ = 1.0(3)° and φ = 51(8)°) of the title compound show that the cyclohexane ring adopts a chair conformation. The molecular conformation of the title compound is stabilized by intramolecular hydrogen bonds (N2-H2⋅⋅⋅Cl1, N2-H2⋅⋅⋅O1, and C2-H2A⋅⋅⋅S1) and intermolecular hydrogen bonds (N1-H1⋅⋅⋅S1ⁱ and C9-HA⋅⋅⋅S1ⁱi: 2-x, 2-y, 1-z). The intramolecular hydrogen bonds (N2-H2⋅⋅⋅O1 and C2-H2A⋅⋅⋅S1) are also form two pseudo-six-membered rings. Density functional theory optimized structure in the gaseous phase at B3LYP/6-311G(d,p) level of theory has been compared with the experimentally defined molecular structure. The molecular orbitals HOMO and LUMO with the energy gap for the title compound are calculated and the estimated energy gap (ΔE) between the HOMO and LUMO energies levels of the title compound is 3.5399 eV, which implies that the title molecule is very reactive. The Hirshfeld surface analysis reveals that the most important contributions to crystal packing are from H···H (49.0%), H···C/C···H (12.5%), H···Cl/Cl···H (10.9%), and H···S/S···H (10.0%) interactions. The energy-framework calculations are used to analyze and visualize the three-dimensional topology of the crystal packing. The intermolecular energy analysis confirmed a significant contribution of dispersion to the stabilization of molecular packings in the title compound.