Akila Shanmugasundaram, Vidhyasagar Thankakan, Winfred Jebaraj John Peter, Thiruvalluvar Aravazhi Amalan, Rajeswari Krishnan
Department of Chemistry, Annamalai University, Annamalai Nagar 608 002, Tamil Nadu, India.
Department of Chemistry, St. John's College, Palayamkottai 627 002, Tamil Nadu, India.
Acta Crystallogr E Crystallogr Commun. 2023 Nov 30;79(Pt 12):1212-1217. doi: 10.1107/S2056989023010162. eCollection 2023 Dec 1.
In the title compound, CHClNO, the seven-membered 1,4-diazepane ring adopts a chair conformation while the 4-chloro-phenyl substituents adopt equatorial orientations. The chloro-phenyl ring at position 7 is disordered over two positions [site occupancies 0.480 (16):0.520 (16)]. The dihedral angle between the two benzene rings is 63.0 (4)°. The methyl groups at position 3 have an axial and an equatorial orientation. The compound exists as a dimer exhibiting inter-molecular N-H⋯O hydrogen bonding with (8) graph-set motifs. The crystal structure is further stabilized by C-H⋯O hydrogen bonds together with two C-Cl⋯π (ring) inter-actions. The geometry was optimized by DFT using the B3LYP/6-31 G(d,p) level basis set. In addition, the HOMO and LUMO energies, chemical reactivity parameters and mol-ecular electrostatic potential were calculated at the same level of theory. Hirshfeld surface analysis indicated that the most important contributions to the crystal packing are from H⋯H (45.6%), Cl⋯H/H⋯Cl (23.8%), H⋯C/C⋯H (12.6%), H⋯O/O⋯H (8.7%) and C⋯Cl/Cl⋯C (7.1%) inter-actions. Analysis of the inter-action energies showed that the dispersion energy is greater than the electrostatic energy. A crystal void volume of 237.16 Å is observed. A mol-ecular docking study with the human oestrogen receptor 3ERT protein revealed good docking with a score of -8.9 kcal mol.
在标题化合物CHClNO中，七元1,4 - 二氮杂环庚烷环呈椅式构象，而4 - 氯苯基取代基呈平伏取向。7位的氯苯环在两个位置上无序 [占有率 0.480 (16):0.520 (16)]。两个苯环之间的二面角为63.0 (4)°。3位的甲基具有一个轴向和一个平伏取向。该化合物以二聚体形式存在，表现出分子间N - H⋯O氢键，具有 (8) 图集模式。晶体结构通过C - H⋯O氢键以及两个C - Cl⋯π (环) 相互作用进一步稳定。使用B3LYP/6 - 31 G(d,p) 基组水平通过DFT对几何结构进行了优化。此外，在相同理论水平下计算了最高占据分子轨道（HOMO）和最低未占据分子轨道（LUMO）能量、化学反应性参数和分子静电势。 Hirshfeld表面分析表明，对晶体堆积最重要的贡献来自H⋯H (45.6%)、Cl⋯H/H⋯Cl (23.8%)、H⋯C/C⋯H (12.6%)、H⋯O/O⋯H (8.7%) 和C⋯Cl/Cl⋯C (7.1%) 相互作用。相互作用能分析表明，色散能大于静电能。观察到晶体空穴体积为237.16 Å。与人类雌激素受体3ERT蛋白的分子对接研究显示对接良好，得分 - 8.9 kcal mol。
