Crystal structure, Hirshfeld surface analysis and interaction energy and DFT studies of 3-{(2Z)-2-[(2,4-dichlorophenyl)methylidene]-3-oxo-3,4-dihydro-2H-1,4-benzothiazin-4-yl}propanenitrile

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Kheira Sebbar N., Hni B., HÖKELEK T., Jaouhar A., Labd Taha M., Mague J. T., ...Daha Fazla

ACTA CRYSTALLOGRAPHICA SECTION E-CRYSTALLOGRAPHIC COMMUNICATIONS, cilt.75, ss.721-733, 2019 (ESCI) identifier identifier identifier

Özet

The title compound, C18H12Cl2N2OS, consists of a dihydrobenzothiazine unit linked by a -CH group to a 2,4-dichlorophenyl substituent, and to a propanenitrile unit is folded along the S center dot center dot center dot N axis and adopts a flattened-boat conformation. The propanenitrile moiety is nearly perpendicular to the mean plane of the dihydrobenzothiazine unit. In the crystal, C-H-Bnz center dot center dot center dot N-Prpnit and C-H-Prpnit center dot center dot center dot O-Thz (Bnz = benzene, Prpnit = propanenitrile and Thz = thiazine) hydrogen bonds link the molecules into inversion dimers, enclosing R-2(2) (16) and R-2(2)(12) ring motifs, which are linked into stepped ribbons extending along [110]. The ribbons are linked in pairs by complementary C=O center dot center dot center dot Cl interactions. pi-pi contacts between the benzene and phenyl rings, [centroid-centroid distance = 3.974 (1) angstrom] may further stabilize the 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 (23.4%), H center dot center dot center dot Cl/Cl center dot center dot center dot H (19.5%), H center dot center dot center dot C/C center dot center dot center dot H (13.5%), H center dot center dot center dot N/N center dot center dot center dot H (13.3%), C center dot center dot center dot C (10.4%) and H center dot center dot center dot O/O center dot center dot center dot H (5.1%) interactions. Hydrogen bonding and van der Waals interactions are the dominant interactions in the crystal packing. Computational chemistry calculations indicate that the two independent C-H-Bnz center dot center dot center dot N-Prpnit and CHPrpnit-O-Thz hydrogen bonds in the crystal impart about the same energy (ca 43 kJ mol(-1)). 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.