Crystal structure, Hirshfeld surface analysis, interaction energy and DFT studies of (2Z)-2-(2,4-dichlorobenzylidene)-4-nonyl-3,4-dihydro-2H-1,4-benzothiazin-3-one


Hni B., Sebbar N. K. , HÖKELEK T. , Redouane A., Mague J. T. , Ahabchane N. H. , ...More

ACTA CRYSTALLOGRAPHICA SECTION E-CRYSTALLOGRAPHIC COMMUNICATIONS, vol.76, pp.281-295, 2020 (Journal Indexed in ESCI) identifier identifier identifier

  • Publication Type: Article / Article
  • Volume: 76
  • Publication Date: 2020
  • Doi Number: 10.1107/s2056989020001036
  • Title of Journal : ACTA CRYSTALLOGRAPHICA SECTION E-CRYSTALLOGRAPHIC COMMUNICATIONS
  • Page Numbers: pp.281-295

Abstract

The title compound, C24H27Cl2NOS, contains 1,4-benzothiazine and 2,4-dichlorophenylmethylidene units in which the dihydrothiazine ring adopts a screw-boat conformation. In the crystal, intermolecular C-H-Bnz center dot center dot center dot O-Thz (Bnz = benzene and Thz = thiazine) hydrogen bonds form chains of molecules extending along the a-axis direction, which are connected to their inversion-related counterparts by C-H-Bnz center dot center dot center dot Cl-Dchlphy (Dchlphy = 2,4-dichlorophenyl) hydrogen bonds and C-H-Dchlphy center dot center dot center dot pi(ring) interactions. These double chains are further linked by C-H-Dchlphy center dot center dot center dot O-Thz hydrogen bonds, forming stepped layers approximately parallel to (012). The Hirshfeld surface analysis of the crystal structure indicates that the most important contributions for the crystal packing are from H center dot center dot center dot H (44.7%), C center dot center dot center dot H/H center dot center dot center dot C (23.7%), Cl center dot center dot center dot H/H center dot center dot center dot Cl (18.9%), O center dot center dot center dot H/H center dot center dot center dot O (5.0%) and S center dot center dot center dot H/H center dot center dot center dot S (4.8%) interactions. Hydrogen-bonding and van der Waals interactions are the dominant interactions in the crystal packing. Computational chemistry indicates that in the crystal, C-H-Dchlphy center dot center dot center dot OThz, C-H-Bnz center dot center dot center dot O-Thz and C-H-Bnz center dot center dot center dot Cl-Dchlphy hydrogen-bond energies are 134.3, 71.2 and 34.4 kJ mol(-1), respectively. Density functional theory (DFT) optimized structures at the B3LYP/6-311 G(d,p) level are compared with the experimentally determined molecular structure in the solid state. The HOMO-LUMO behaviour was elucidated to determine the energy gap. The two carbon atoms at the end of the nonyl chain are disordered in a 0.562 (4)/0.438 (4) ratio.