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

Abstract

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...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—HBnz...NPrpnit and C—HPrpnit...OThz (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...Cl interactions. π–π contacts between the benzene and phenyl rings, [centroid–centroid distance = 3.974 (1) Å] 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...H (23.4%), H...Cl/Cl...H (19.5%), H...C/C...H (13.5%), H...N/N...H (13.3%), C...C (10.4%) and H...O/O...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—HBnz...NPrpnit and C—HPrpnit...OThz 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.

Facile Ultrasound‐Based Synthesis, SC‐XRD, DFT Exploration of the Substituted Acyl‐Hydrazones: An Experimental and Theoretical Slant towards Supramolecular Chemistry

“…The disintegration of two‐dimensional fingerprint contributed the inter and intera‐molecular interactions, usually can be found in the chemical structures [19–20,21,22] . In our study, powerful intermolecular associations observed within H−H as 30.8 % and 34.0 % for CPPAH and MBPAH , respectively (Figure 5).…”

Exploration of CH⋯F & CF⋯H mediated supramolecular arrangements into fluorinated terphenyls and theoretical prediction of their third-order nonlinear optical response

“…Each point of the Hirshfeld surface contained two kinds of critical distances viz de and di, these were the distances from that point to the adjacent nucleus, outward and inward to the surface of molecule respectively. 42,43 Hirshfeld surface analysis for 1, 2 and 3 was done to estimate the strength of intermolecular interactions. The Hirshfeld surface structure for compounds 1, 2 and 3 are arranged in Fig.…”

Stabilization of Supramolecular Assembly of N‐Substituted Benzylidene Acetohydrazide Analogs by Non‐Covalent Interactions: A Concise Experimental and Theoretical Approach

“…[24] According to Bader, who proposed QT-AIM, this indicated a significant interaction between the atoms. [25] The non-covalent interactions are mainly characterized by their positive laplacian of density value (r 2 1(e/a 5 )) which indicates non-covalent interactions. The interactions with positive valued r 2 1 are listed in Table 2.…”