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

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Sebbar N. K., Hni B., HÖKELEK T., Taha M. L., Mague J. T., El Ghayati L., ...Daha Fazla

ACTA CRYSTALLOGRAPHICA SECTION E-CRYSTALLOGRAPHIC COMMUNICATIONS, cilt.75, ss.1650-1662, 2019 (ESCI) identifier identifier identifier

Özet

The title compound, C22H15Cl2NOS, contains 1,4-benzothiazine and 2,4-dichlorobenzylidene units, where 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 corrugated chains extending along the b-axis direction which are connected into layers parallel to the be plane by intermolecular C-H-Methy center dot center dot center dot S-Thz (Methy = methylene) hydrogen bonds, enclosing R-4(4)(22) ring motifs. Offset pi-stacking interactions between 2,4-dichlorophenyl rings [centroid-centroid = 3.7701 (8) angstrom] and pi-interactions which are associated by C-H-Bnz center dot center dot center dot pi(ring) and C-H-Dehlphy center dot center dot center dot pi(ring) (Dchlphy = 2,4-dichlorophenyl) interactions may be effective in the stabilization of the crystal structure. 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 (29.1%), H center dot center dot center dot C/C center dot center dot center dot H (27.5%), H center dot center dot center dot Cl/Cl center dot center dot center dot H (20.6%) and O center dot center dot center dot H/H center dot center dot center dot O (7.0%) interactions. Hydrogen-bonding and van der Waals interactions are the dominant interactions in the crystal packing. Computational chemistry indicates that in the crystal, the C-H-Bnz center dot center dot center dot O-Thz and C-H-Methy center dot center dot center dot S-Thz hydrogen-bond energies are 55.0 and 27.1 kJ mol(-1), respectively. Density functional theory (DFT) optimized structures at the B3LYP/6-311G(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.