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

Sebbar, N.K.; Hni, B.; Hökelek, T.; Labd Taha, M.; Mague, J.T.; El Ghayati, L.; Essassi, E.M.

doi:10.1107/S2056989019013586

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ISSN: 2056-9890

Volume 75| Part 11| November 2019| Pages 1650-1656

https://doi.org/10.1107/S2056989019013586

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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

Nada Kheira Sebbar,^a,^b Brahim Hni,^b Tuncer Hökelek,^c Mohamed Labd Taha,^a Joel T. Mague,^d Lhoussaine El Ghayati ^b ^* and El Mokhtar Essassi ^b

^aLaboratoire de Chimie Appliquée et Environnement, Equipe de Chimie Bioorganique Appliquée, Faculté des Sciences, Université Ibn Zohr, Agadir, Morocco, ^bLaboratoire de Chimie Organique Hétérocyclique URAC 21, Pôle de Compétence Pharmacochimie, Av. Ibn Battouta, BP 1014, Faculté des Sciences, Université Mohammed V, Rabat, Morocco, ^cDepartment of Physics, Hacettepe University, 06800 Beytepe, Ankara, Turkey, and ^dDepartment of Chemistry, Tulane University, New Orleans, LA 70118, USA
^*Correspondence e-mail: elghayatilhoussaine2018@gmail.com

Edited by A. J. Lough, University of Toronto, Canada (Received 24 September 2019; accepted 4 October 2019; online 22 October 2019)

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⋯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 bc plane by intermolecular C—H_Methy⋯S_Thz (Methy = methylene) hydrogen bonds, enclosing R₄⁴(22) ring motifs. Offset π-stacking interactions between 2,4-dichlorophenyl rings [centroid–centroid = 3.7701 (8) Å] and π-interactions which are associated by C—H_Bnz⋯π(ring) and C—H_Dchlphy⋯π(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⋯H (29.1%), H⋯C/C⋯H (27.5%), H⋯Cl/Cl⋯H (20.6%) and O⋯H/H⋯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⋯O_Thz and C—H_Methy⋯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.

Keywords: crystal structure; dihydrothiazine; hydrogen bond; π-stacking; Hirshfeld surface.

CCDC references: 1957875; 1957875

1. Chemical context

1,4-Benzothiazine derivatives constitute an important class of heterocyclic systems. These molecules exhibit a wide range of biological applications, indicating the fact that the 1,4-benzothiazine moiety is a template potentially useful in medicinal chemistry research and therapeutic applications, such as the anti-inflammatory (Trapani et al., 1985 ; Gowda et al., 2011 ), antipyretic (Warren & Knaus, 1987 ), antimicrobial (Armenise et al., 2012 ; Rathore & Kumar, 2006 ), antiviral (Malagu et al., 1998 ), anticancer (Gupta et al., 1985 ; Gupta & Gupta, 1991 ) and anti-oxidant (Zia-ur-Rehman et al., 2009 ) areas. They have also been reported as precursors for the syntheses of new compounds (Sebbar et al., 2015a ; Vidal et al., 2006 ) possessing antidiabetic (Tawada et al., 1990 ) and anticorrosion activities (Ellouz et al., 2016a ,b ; Sebbar et al., 2016a ). They also possess biological properties (Hni et al., 2019a ,b ; Sebbar et al., 2017 ; Ellouz et al., 2017a ,b , 2018 ). As a continuation of our research on the development of N-substituted 1,4-benzothiazine derivatives and the evaluation of their potential pharmacological activities, we report here the synthesis of (2Z)-4-benzyl-2-(2,4-dichlorobenzylidene)-2H-1,4-benzothiazin-3(4H)-one, (I), by the reaction of benzyl chloride with (Z)-2-(2,4-dichlorobenzylidene)-2H-1,4-benzothiazin-3(4H)-one and potassium carbonate in the presence of tetra-n-butylammonium bromide (as catalyst). The molecular and crystal structures, together with the Hirshfeld surface analysis, the intermolecular interaction energies and density functional theory (DFT) computational calculations were carried out at the B3LYP/6-311G(d,p) and B3LYP/6-311G(d,p) levels, respectively, for (I) (see Scheme 1).

2. Structural commentary

The title compound, (I), contains 1,4-benzothiazine and 2,4-dichlorobenzylidene units (Fig. 1), where the dihydrothiazine ring, B (atoms S1/N1/C1/C6–C8), adopts a screw-boat conformation with puckering parameters (Cremer & Pople, 1975 ) of Q_T = 0.4331 (10) Å, θ = 68.34 (16)° and φ = 333.95 (17)°. The planar rings A (C1–C6), C (C10–C15) and D (C17–C22) are oriented at dihedral angles of A/C = 60.49 (4)°, A/D = 79.69 (4)° and C/D = 41.29 (4)°. Atoms Cl1 and Cl2 are −0.0156 (3) and 0.0499 (4) Å from ring C and so are almost coplanar.

Figure 1
The molecular structure of the title compound with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.

3. Supramolecular features

In the crystal, intermolecular C—H_Bnz⋯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 bc plane by intermolecular C—H_Methy⋯S_Thz (Methy = methylene) hydrogen bonds, enclosing $[R_{4}^{4}]$ (22) ring motifs (Bernstein et al., 1995 ) (Table 1 and Fig. 2). Offset π-stacking interactions between 2,4-dichlorophenyl rings C [atoms C10–C15; Cg3⋯Cg3ⁱ, where Cg3 is the centroid of ring C; symmetry code: (i) −x, −y + 1, −z + 1], may further stabilize the structure, with a centroid–centroid distance of 3.7701 (8) Å, together with π-interactions, i.e. C—H_Bnz⋯π(ring) and C—H_Dchlphy⋯π(ring) (Dchlphy = 2,4-dichlorophenyl). The Hirshfeld surface analysis of the crystal structure indicates that the most important contributions for the crystal packing are from H⋯H (29.1%), H⋯C/C⋯H (27.5%), H⋯Cl/Cl⋯H (20.6%) and O⋯H/H⋯O (7.0%) interactions. Hydrogen-bonding and van der Waals interactions are the dominant interactions in the crystal packing.

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 and Cg4 are the centroids of rings A (C1–C6) and D (C17–C22), respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C4—H4⋯O1^ix	0.936 (19)	2.51 (2)	3.3346 (17)	147.7 (15)
C16—H16B⋯S1^v	0.945 (16)	2.852 (16)	3.7011 (13)	149.9 (12)
C3—H3⋯Cg4^ix	0.938 (17)	2.901 (17)	3.6428 (15)	136.8 (13)
C14—H14⋯Cg4^x	0.971 (19)	2.710 (18)	3.5593 (15)	146.8 (14)
C18—H18⋯Cg1^xi	0.979 (18)	2.969 (18)	3.6759 (16)	130.0 (13)
Symmetry codes: (v) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (ix) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (x) $[x-1, -y-{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (xi) $[x, -y-{\script{1\over 2}}, z-{\script{3\over 2}}]$ .

Figure 2
A partial packing diagram, viewed along the a-axis direction, with C—H_Bnz⋯O_Thz and C—H_Methy⋯S_Thz (Bnz = benzene, Thz = thiazine and Methy = methylene) hydrogen bonds shown, respectively, as black and light-purple dashed lines.

4. Hirshfeld surface analysis

In order to visualize the intermolecular interactions in the crystal of (I), a Hirshfeld surface (HS) analysis (Hirshfeld, 1977 ; Spackman & Jayatilaka, 2009 ) was carried out using CrystalExplorer (Version 17.5; Turner et al., 2017 ). In the HS plotted over d_norm (Fig. 3), the white surface indicates contacts with distances equal to the sum of the van der Waals radii, and the red and blue colours indicate distances shorter (in close contact) or longer (distinct contact) than the van der Waals radii, respectively (Venkatesan et al., 2016 ). The bright-red spots appearing near atoms O1, S1 and H4 indicate their roles as the respective donors and/or acceptors; they also appear as blue and red regions corresponding to positive and negative potentials on the HS mapped over electrostatic potential (Spackman et al., 2008 ; Jayatilaka et al., 2005 ), as shown in Fig. 4. The blue regions indicate the positive electrostatic potential (hydrogen-bond donors), while the red regions indicate the negative electrostatic potential (hydrogen-bond acceptors). The shape-index of the HS is a tool to visualize the π–π stacking by the presence of adjacent red and blue triangles; if there are no adjacent red and/or blue triangles, then there are no π–π interactions. Fig. 5 clearly suggest that there are π–π interactions in (I). The overall two-dimensional (2D) fingerprint plot (Fig. 6a) and those delineated into H⋯H, H⋯C/C⋯H, H⋯Cl/Cl⋯H, O⋯H/H⋯O, C⋯C, S⋯H/H⋯S and Cl⋯C/C⋯Cl contacts (McKinnon et al., 2007 ) are illustrated in Figs. 6(b)–(h), respectively, together with their relative contributions to the Hirshfeld surface. The most important interaction is H⋯H, contributing 29.1% to the overall crystal packing, which is reflected in Fig. 6(b) as widely scattered points of high density due to the large hydrogen content of the molecule with the tip at d_e = d_i = 1.17 Å, due to the short interatomic H⋯H contacts (Table 2). In the presence of C—H⋯π interactions, the pairs of characteristic wings resulting in the fingerprint plot delineated into H⋯C/C⋯H contacts (Fig. 6c), with a 27.5% contribution to the HS, arises from the H⋯C/C⋯H contacts (Table 2) and are viewed as pairs of spikes with the tips at d_e + d_i = 2.82 and 2.78 Å for thin and thick spikes, respectively. The pair of scattered points of the wings resulting in the fingerprint plots delineated into H⋯Cl/Cl⋯H (Fig. 6d), with a 20.6% contribution to the HS, has a symmetrical distribution of points with the edges at d_e + d_i = 2.78 Å arising from the H⋯Cl/Cl⋯H contacts (Table 2). The pair of characteristic wings resulting in the fingerprint plot delineated into O⋯H/H⋯O contacts (Fig. 6e), with a 7.0% contribution to the HS, arises from the O⋯H/H⋯O contacts (Table 2) and is viewed as a pair of spikes with the tips at d_e + d_i = 2.35 Å. The C⋯C contacts (Fig. 6f) have an arrow-shaped distribution of points with the tip at d_e = d_i = 1.7 Å. Finally, the characteristic wings resulting in the fingerprint plots delineated into S⋯H/H⋯S and Cl⋯C/C⋯Cl contacts (Figs. 6g and 6h), with 4.0 and 2.2% contributions to the HS, arise from the S⋯H/H⋯S and Cl⋯C/C⋯Cl contacts (Table 2) and are viewed with the tips at d_e = d_i = 2.70 Å and d_e + d_i = 3.46 Å, respectively.

Table 2
Selected interatomic distances (Å)

Cl1⋯Cl1ⁱ	3.2439 (5)	C6⋯C22	3.4830 (18)
Cl1⋯C14ⁱⁱ	3.4981 (14)	C6⋯C12^v	3.5828 (18)
Cl1⋯H9	2.647 (16)	C7⋯C22	3.4391 (18)
Cl2⋯H19ⁱⁱⁱ	2.96 (2)	C10⋯C12ⁱⁱ	3.4871 (18)
Cl2⋯H9ⁱⁱ	3.044 (16)	C14⋯C20^iv	3.572 (2)
Cl2⋯H4^iv	3.138 (18)	C5⋯H16A	2.563 (16)
S1⋯Cl2^v	3.5832 (5)	C6⋯H22	2.904 (15)
S1⋯Cl2^v	3.5832 (5)	C8⋯H15	2.929 (18)
S1⋯N1	3.0801 (11)	C16⋯H5	2.556 (18)
S1⋯C15	3.1625 (14)	C17⋯H5	2.829 (18)
S1⋯C13^v	3.6033 (13)	C18⋯H3^vi	2.998 (17)
S1⋯H15	2.578 (18)	C21⋯H12ⁱ	2.845 (18)
O1⋯C17	3.2096 (16)	H14⋯C20^iv	2.964 (18)
O1⋯C4^vi	3.3346 (17)	H14⋯C21^iv	2.899 (18)
O1⋯H9	2.406 (16)	H14⋯C22^iv	2.990 (18)
O1⋯H16B	2.345 (16)	H15⋯C19^iv	2.951 (18)
O1⋯H4^vi	2.51 (2)	H16B⋯S1^v	2.852 (16)
N1⋯S1	3.0801 (11)	H16B⋯C1^v	2.973 (16)
N1⋯H22	2.552 (15)	H18⋯C6^v	2.934 (19)
C1⋯C12^v	3.4639 (18)	H5⋯H16A	2.16 (2)
C1⋯C13^v	3.4372 (18)	H12⋯H21ⁱ	2.46 (3)
C2⋯C12^v	3.541 (2)	H15⋯H21^viii	2.51 (3)
C3⋯C3^vii	3.485 (2)	H16B⋯H18	2.51 (2)
C5⋯C22	3.4988 (19)	H18⋯H22^v	2.53 (2)
C5⋯C17	3.4201 (18)
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) -x, -y+1, -z+1; (iii) x-1, y, z+1; (iv) $[x-1, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (v) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (vi) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (vii) -x+1, -y, -z+1; (viii) x-1, y, z.

Figure 3
View of the 3D Hirshfeld surface of the title compound, plotted over d_norm in the range −0.1634 to 1.5051 a.u.

Figure 4
View of the 3D Hirshfeld surface of the title compound, plotted over electrostatic potential energy in the range −0.0500 to 0.0500 a.u., using the STO-3G basis set at the Hartree–Fock level of theory. Hydrogen-bond donors and acceptors are shown as blue and red regions around the atoms corresponding to positive and negative potentials, respectively.

Figure 5
Hirshfeld surface of the title compound plotted over shape-index.

Figure 6
The full 2D fingerprint plots for the title compound, showing (a) all interactions, and delineated into (b) H⋯H, (c) H⋯C/C⋯H, (d) H⋯Cl/Cl⋯H, (e) O⋯H/H⋯O, (f) C⋯C, (g) S⋯H/H⋯S and (h) Cl⋯C/C⋯Cl interactions. The d_i and d_e values are the closest internal and external distances (in Å) from given points on the Hirshfeld surface contacts.

The Hirshfeld surface representations with the function d_norm plotted onto the surface are shown for the H⋯H, H⋯C/C⋯H, H⋯Cl/Cl⋯H, O⋯H/H⋯O, C⋯C and S⋯H/H⋯S interactions in Figs. 7(a)–(f), respectively.

Figure 7
The Hirshfeld surface representations with the function d_norm plotted onto the surface for (a) H⋯H, (b) H⋯C/C⋯H, (c) H⋯Cl/Cl⋯H, (d) O⋯H/H⋯O, (e) C⋯C and (f) S⋯H/H⋯S interactions.

The Hirshfeld surface analysis confirms the importance of H-atom contacts in establishing the packing. The large number of H⋯H, H⋯C/C⋯H, H⋯Cl/Cl⋯H and O⋯H/H⋯O interactions suggest that van der Waals interactions and hydrogen bonding play the biggest roles in the crystal packing (Hathwar et al., 2015 ).

5. Interaction energy calculations

The intermolecular interaction energies are calculated using CE–B3LYP/6-31G(d,p) energy model available in CrystalExplorer (CE) (Version 17.5; Turner et al., 2017), where a cluster of molecules would need to be generated by applying crystallographic symmetry operations with respect to a selected central molecule within a default radius of 3.8 Å (Turner et al., 2014 ). The total intermolecular energy (E_tot) is the sum of the electrostatic (E_ele), polarization (E_pol), dispersion (E_dis) and exchange-repulsion (E_rep) energies (Turner et al., 2015 ), with scale factors of 1.057, 0.740, 0.871 and 0.618, respectively (Mackenzie et al., 2017 ). Hydrogen-bonding interaction energies (in kJ mol⁻¹) were calculated as −20.3 (E_ele), −2.6 (E_pol), −79.4 (E_dis), 60.7 (E_rep) and −55.0 (E_tot) for C—H_Bnz⋯O_Thz hydrogen-bonding interactions, and −5.8 (E_ele), −1.0 (E_pol), −51.0 (E_dis), 39.3 (E_rep) and −27.1 (E_tot) for C—H_Methy⋯S_Thz hydrogen-bonding interactions.

6. DFT calculations

The optimized structure of (I) in the gas phase was generated theoretically via density functional theory (DFT) using standard B3LYP functional and 6-311G(d,p) basis-set calculations (Becke, 1993 ), as implemented in GAUSSIAN09 (Frisch et al., 2009 ). The theoretical and experimental results were in good agreement (Table 3). The highest-occupied molecular orbital (HOMO), acting as an electron donor, and the lowest-unoccupied molecular orbital (LUMO), acting as an electron acceptor, are very important parameters for quantum chemistry. When the energy gap is small, the molecule is highly polarizable and has high chemical reactivity. The DFT calculations provide some important information on the reactivity and site selectivity of the molecular framework. E_HOMO and E_LUMO clarifying the inevitable charge exchange collaboration inside the studied material, electronegativity (χ), hardness (η), potential (μ), electrophilicity (ω) and softness (σ) are recorded in Table 4. The significance of η and σ is to evaluate both the reactivity and stability. The electron transition from the HOMO to the LUMO energy level is shown in Fig. 8. The HOMO and LUMO are localized in the plane extending from the whole molecule. The energy band gap (ΔE = E_LUMO – E_HOMO) of the molecule was about 5.3364 eV, and the frontier molecular orbital (FMO) energies, E_HOMO and E_LUMO, were −8.2479 and −2.9115 eV, respectively.

Table 3
Comparison of the selected (X-ray and DFT) geometric data (Å, °)

Bonds/angles	X-ray	B3LYP/6–311G(d,p)
Cl1—C11	1.7357 (13)	1.80981
Cl2—C13	1.7382 (13)	1.80489
S1—C8	1.7525 (12)	1.80120
S1—C1	1.7561 (13)	1.82629
O1—C7	1.2228 (16)	1.23968
N1—C7	1.3759 (16)	1.38157
N1—C6	1.4192 (16)	1.41776
N1—C16	1.4661 (16)	1.47048
C8—S1—C1	100.14 (6)	98.69028
C7—N1—C6	125.51 (10)	124.58623
C7—N1—C16	115.14 (10)	116.12685
C6—N1—C16	119.20 (10)	119.26679
C2—C1—C6	120.71 (12)	121.24260
C2—C1—S1	117.26 (10)	117.48822
C6—C1—S1	122.02 (10)	121.26667

Table 4
Calculated energies.

Molecular Energy (a.u.) (eV)	Compound (I)
Total Energy TE (eV)	−62249, 6662
E_HOMO (eV)	−8.2479
E_LUMO (eV)	−2.9115
Gap ΔE (eV)	5.3364
Dipole moment, μ (Debye)	3.4723
Ionization potential, I (eV)	8.2479
Electron affinity, A	2.9115
Electro negativity, χ	5.3364
Hardness, η	2.6682
Electrophilicity index, ω	5.8340
Softness, σ	0.3748
Fraction of electron transferred, ΔN	0.2662

Figure 8
The energy band gap of the title compound.

7. Database survey

A search in the Cambridge Structural Database (Groom et al., 2016 ; updated to June 2019) for compounds containing the fragment II (with R₁ = Ph and R₂ = C; see Scheme 2) gave 14 hits. With R₁ = Ph and R₂ = CH₂C≡CH (IIa) (Sebbar et al., 2014a ), CH₂COOH (IIb) (Sebbar et al., 2016c ), 2-(2-oxo-1,3-oxazolidin-3-yl)ethyl (IIc) (Sebbar et al., 2016b ) and (3-phenyl-4,5-dihydro-1,2-oxazol-5-yl)methyl (IIf) (Sebbar et al., 2015b )] (Scheme 2), there are other examples with R₁ = 4-FC₆H₄ and R₂ = CH₂C≡CH (IIa) (Hni et al., 2019a), R₁ = 4-ClC₆H₄ and R₂ = CH₂Ph2 (IId) (Ellouz et al., 2016c ), and R₁ = 2-ClC₆H₄ and R₂ = CH₂C≡CH (IIa) (Sebbar et al., 2017) (Scheme 2). In all compounds, the configuration about the benzylidene-group C=CHC₆H₅ bond is Z, and in the majority of these, the heterocyclic ring is quite nonplanar, with the dihedral angle between the plane defined by the benzene ring plus the N and S atoms, and that defined by the N and S atoms and the other two C atoms separating them ranging from ca 29 (for IIa) to 36° (for IIf). The other two (IIa and IIc) have the benzothiazine unit nearly planar, with corresponding dihedral angles of ca 3–4°.

8. Synthesis and crystallization

To a solution of (Z)-2-(2,4-dichlorobenzylidene)-2H-1,4-benzothiazin-3(4H)-one (3.21 mmol), benzyl chloride (6.52 mmol) and potassium carbonate (6.51 mmol) in dimethylformamide (DMF; 17 ml) was added a catalytic amount of tetra-n-butylammonium bromide (0.33 mmol). The mixture was stirred for 24 h. The solid material was removed by filtration and the solvent evaporated under vacuum. The solid product was purified by recrystallization from ethanol to afford colourless crystals in 82% yield.

9. Refinement

The experimental details, including the crystal data, data collection and refinement, are summarized in Table 5. H atoms were located in a difference Fourier map and refined freely.

Table 5
Experimental details

Crystal data
Chemical formula	C₂₂H₁₅Cl₂NOS
M_r	412.31
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	150
a, b, c (Å)	9.0373 (7), 16.6798 (13), 12.511 (1)
β (°)	95.982 (2)
V (Å³)	1875.6 (3)
Z	4
Radiation type	Cu Kα
μ (mm⁻¹)	4.25
Crystal size (mm)	0.15 × 0.13 × 0.09

Data collection
Diffractometer	Bruker D8 VENTURE PHOTON 100 CMOS
Absorption correction	Numerical (SADABS; Krause et al., 2015 )
T_min, T_max	0.59, 0.70
No. of measured, independent and observed [I > 2σ(I)] reflections	48886, 3847, 3650
R_int	0.038
(sin θ/λ)_max (Å⁻¹)	0.625

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.026, 0.070, 1.05
No. of reflections	3847
No. of parameters	304
H-atom treatment	All H-atom parameters refined
Δρ_max, Δρ_min (e Å⁻³)	0.22, −0.26
Computer programs: APEX3 (Bruker, 2016 ), SAINT (Bruker, 2016), SHELXT (Sheldrick, 2015a ), SHELXL2018 (Sheldrick, 2015b ), DIAMOND (Brandenburg & Putz, 2012 ) and SHELXTL (Bruker, 2016).

Supporting information

CCDC references: 1957875; 1957875

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S2056989019013586/lh5925sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989019013586/lh5925Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989019013586/lh5925Isup3.cdx

checkCIF report

Computing details top

Data collection: APEX3 (Bruker, 2016); cell refinement: SAINT (Bruker, 2016); data reduction: SAINT (Bruker, 2016); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015b); molecular graphics: DIAMOND (Brandenburg & Putz, 2012); software used to prepare material for publication: SHELXTL (Bruker, 2016).

(2Z)-4-Benzyl-2-(2,4-dichlorobenzylidene)-2H-1,4-benzothiazin-3(4H)-one top

Crystal data top

C₂₂H₁₅Cl₂NOS	F(000) = 848
M_r = 412.31	D_x = 1.460 Mg m⁻³
Monoclinic, P2₁/c	Cu Kα radiation, λ = 1.54178 Å
a = 9.0373 (7) Å	Cell parameters from 9943 reflections
b = 16.6798 (13) Å	θ = 4.4–43.5°
c = 12.511 (1) Å	µ = 4.25 mm⁻¹
β = 95.982 (2)°	T = 150 K
V = 1875.6 (3) Å³	Block, colourless
Z = 4	0.14 × 0.13 × 0.09 mm

Data collection top

Bruker D8 VENTURE PHOTON 100 CMOS diffractometer	3847 independent reflections
Radiation source: INCOATEC IµS micro-focus source	3650 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.038
Detector resolution: 10.4167 pixels mm^-1	θ_max = 74.6°, θ_min = 4.4°
ω scans	h = −11→11
Absorption correction: numerical (SADABS; Krause et al., 2015)	k = −20→20
T_min = 0.59, T_max = 0.70	l = −15→15
48886 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F² > 2σ(F²)] = 0.026	All H-atom parameters refined
wR(F²) = 0.070	w = 1/[σ²(F_o²) + (0.0379P)² + 0.6937P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max = 0.001
3847 reflections	Δρ_max = 0.22 e Å⁻³
304 parameters	Δρ_min = −0.26 e Å⁻³
0 restraints

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > 2sigma(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Cl1	0.32725 (3)	0.51603 (2)	0.51778 (3)	0.03318 (9)
Cl2	−0.08376 (4)	0.45362 (2)	0.78449 (3)	0.03443 (10)
S1	0.15102 (3)	0.21109 (2)	0.37534 (2)	0.02451 (9)
O1	0.29675 (11)	0.36735 (6)	0.18264 (8)	0.0318 (2)
N1	0.36671 (11)	0.23777 (6)	0.20360 (8)	0.0231 (2)
C1	0.29233 (13)	0.14621 (7)	0.34225 (10)	0.0235 (2)
C2	0.30706 (15)	0.07308 (8)	0.39669 (11)	0.0287 (3)
H2	0.2413 (19)	0.0621 (10)	0.4526 (14)	0.033 (4)*
C3	0.41257 (16)	0.01777 (8)	0.37140 (12)	0.0327 (3)
H3	0.4187 (18)	−0.0323 (10)	0.4058 (13)	0.030 (4)*
C4	0.50780 (16)	0.03719 (8)	0.29531 (13)	0.0330 (3)
H4	0.579 (2)	−0.0001 (12)	0.2780 (15)	0.042 (5)*
C5	0.49570 (15)	0.11045 (8)	0.24245 (11)	0.0285 (3)
H5	0.5655 (19)	0.1230 (11)	0.1921 (13)	0.035 (4)*
C6	0.38507 (13)	0.16533 (7)	0.26301 (10)	0.0233 (2)
C7	0.29726 (13)	0.30575 (7)	0.23567 (10)	0.0237 (2)
C8	0.22305 (13)	0.30312 (7)	0.33731 (10)	0.0223 (2)
C9	0.20587 (14)	0.37330 (7)	0.38765 (10)	0.0241 (2)
H9	0.2472 (18)	0.4183 (10)	0.3553 (13)	0.031 (4)*
C10	0.13615 (13)	0.38965 (7)	0.48567 (10)	0.0232 (2)
C11	0.18203 (13)	0.45583 (7)	0.55067 (10)	0.0239 (2)
C12	0.11763 (15)	0.47512 (8)	0.64272 (11)	0.0266 (3)
H12	0.152 (2)	0.5194 (11)	0.6845 (14)	0.040 (5)*
C13	0.00202 (14)	0.42783 (8)	0.67128 (10)	0.0261 (3)
C14	−0.04785 (15)	0.36229 (8)	0.61082 (11)	0.0283 (3)
H14	−0.130 (2)	0.3302 (11)	0.6306 (14)	0.038 (4)*
C15	0.01925 (15)	0.34384 (8)	0.51908 (11)	0.0271 (3)
H15	−0.019 (2)	0.3021 (11)	0.4758 (15)	0.042 (5)*
C16	0.43514 (15)	0.24544 (8)	0.10287 (10)	0.0261 (3)
H16A	0.4342 (18)	0.1915 (10)	0.0694 (13)	0.029 (4)*
H16B	0.3717 (18)	0.2771 (10)	0.0550 (13)	0.027 (4)*
C17	0.59004 (14)	0.28115 (7)	0.11411 (10)	0.0235 (2)
C18	0.65243 (16)	0.30239 (9)	0.02058 (11)	0.0311 (3)
H18	0.593 (2)	0.2943 (11)	−0.0487 (15)	0.039 (5)*
C19	0.79411 (17)	0.33523 (9)	0.02566 (13)	0.0384 (3)
H19	0.835 (2)	0.3503 (12)	−0.0383 (16)	0.050 (5)*
C20	0.87604 (17)	0.34739 (9)	0.12401 (14)	0.0382 (3)
H20	0.973 (2)	0.3695 (12)	0.1271 (15)	0.046 (5)*
C21	0.81497 (16)	0.32701 (8)	0.21707 (13)	0.0334 (3)
H21	0.874 (2)	0.3354 (11)	0.2875 (14)	0.040 (5)*
C22	0.67257 (15)	0.29448 (8)	0.21258 (11)	0.0273 (3)
H22	0.6283 (17)	0.2799 (9)	0.2793 (12)	0.024 (4)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.02604 (16)	0.03290 (17)	0.04160 (19)	−0.00735 (12)	0.00829 (13)	−0.00211 (13)
Cl2	0.03839 (18)	0.03495 (18)	0.03231 (17)	0.00967 (13)	0.01489 (13)	0.00164 (12)
S1	0.02266 (15)	0.02109 (15)	0.03075 (17)	−0.00207 (11)	0.00738 (12)	0.00098 (11)
O1	0.0405 (5)	0.0264 (5)	0.0303 (5)	0.0018 (4)	0.0116 (4)	0.0066 (4)
N1	0.0226 (5)	0.0248 (5)	0.0224 (5)	−0.0006 (4)	0.0050 (4)	0.0000 (4)
C1	0.0225 (6)	0.0217 (6)	0.0261 (6)	−0.0018 (5)	0.0009 (5)	−0.0017 (5)
C2	0.0297 (7)	0.0241 (6)	0.0321 (7)	−0.0029 (5)	0.0017 (5)	0.0022 (5)
C3	0.0349 (7)	0.0215 (6)	0.0406 (8)	0.0005 (5)	−0.0015 (6)	0.0025 (5)
C4	0.0295 (7)	0.0245 (6)	0.0446 (8)	0.0037 (5)	0.0022 (6)	−0.0047 (6)
C5	0.0253 (6)	0.0267 (6)	0.0337 (7)	−0.0007 (5)	0.0044 (5)	−0.0047 (5)
C6	0.0225 (6)	0.0214 (6)	0.0255 (6)	−0.0026 (5)	0.0004 (5)	−0.0020 (5)
C7	0.0223 (6)	0.0241 (6)	0.0247 (6)	−0.0015 (5)	0.0025 (5)	0.0010 (5)
C8	0.0194 (5)	0.0231 (6)	0.0246 (6)	0.0002 (4)	0.0034 (4)	0.0033 (4)
C9	0.0229 (6)	0.0224 (6)	0.0276 (6)	0.0000 (5)	0.0051 (5)	0.0036 (5)
C10	0.0228 (6)	0.0207 (6)	0.0265 (6)	0.0038 (5)	0.0041 (5)	0.0034 (4)
C11	0.0201 (6)	0.0224 (6)	0.0293 (6)	0.0025 (4)	0.0034 (5)	0.0033 (5)
C12	0.0259 (6)	0.0242 (6)	0.0293 (6)	0.0039 (5)	0.0015 (5)	−0.0006 (5)
C13	0.0265 (6)	0.0260 (6)	0.0267 (6)	0.0083 (5)	0.0069 (5)	0.0042 (5)
C14	0.0279 (6)	0.0238 (6)	0.0350 (7)	0.0014 (5)	0.0111 (5)	0.0048 (5)
C15	0.0281 (6)	0.0222 (6)	0.0318 (7)	−0.0001 (5)	0.0075 (5)	0.0002 (5)
C16	0.0273 (6)	0.0315 (7)	0.0196 (6)	−0.0010 (5)	0.0033 (5)	−0.0020 (5)
C17	0.0256 (6)	0.0215 (6)	0.0240 (6)	0.0032 (5)	0.0062 (5)	0.0002 (4)
C18	0.0344 (7)	0.0333 (7)	0.0271 (7)	0.0065 (6)	0.0104 (5)	0.0039 (5)
C19	0.0385 (8)	0.0330 (7)	0.0476 (9)	0.0061 (6)	0.0232 (7)	0.0101 (6)
C20	0.0270 (7)	0.0262 (7)	0.0630 (10)	−0.0002 (5)	0.0123 (6)	0.0026 (6)
C21	0.0290 (7)	0.0262 (7)	0.0442 (8)	−0.0002 (5)	−0.0002 (6)	−0.0042 (6)
C22	0.0294 (6)	0.0261 (6)	0.0265 (6)	−0.0009 (5)	0.0042 (5)	−0.0013 (5)

Geometric parameters (Å, º) top

Cl1—C11	1.7357 (13)	C10—C11	1.4076 (18)
Cl2—C13	1.7382 (13)	C11—C12	1.3814 (18)
S1—C8	1.7525 (12)	C12—C13	1.3854 (19)
S1—C1	1.7561 (13)	C12—H12	0.940 (19)
O1—C7	1.2228 (16)	C13—C14	1.3781 (19)
N1—C7	1.3759 (16)	C14—C15	1.3874 (19)
N1—C6	1.4192 (16)	C14—H14	0.971 (19)
N1—C16	1.4661 (16)	C15—H15	0.928 (19)
C1—C2	1.3967 (18)	C16—C17	1.5143 (18)
C1—C6	1.4000 (18)	C16—H16A	0.993 (17)
C2—C3	1.387 (2)	C16—H16B	0.945 (16)
C2—H2	0.981 (18)	C17—C22	1.3899 (18)
C3—C4	1.387 (2)	C17—C18	1.3965 (18)
C3—H3	0.938 (17)	C18—C19	1.388 (2)
C4—C5	1.388 (2)	C18—H18	0.979 (18)
C4—H4	0.94 (2)	C19—C20	1.383 (2)
C5—C6	1.3990 (18)	C19—H19	0.95 (2)
C5—H5	0.960 (18)	C20—C21	1.382 (2)
C7—C8	1.4988 (17)	C20—H20	0.95 (2)
C8—C9	1.3458 (18)	C21—C22	1.392 (2)
C9—C10	1.4616 (17)	C21—H21	0.993 (18)
C9—H9	0.948 (17)	C22—H22	0.992 (16)
C10—C15	1.4024 (18)

Cl1···Cl1ⁱ	3.2439 (5)	C6···C22	3.4830 (18)
Cl1···C14ⁱⁱ	3.4981 (14)	C6···C12^v	3.5828 (18)
Cl1···H9	2.647 (16)	C7···C22	3.4391 (18)
Cl2···H19ⁱⁱⁱ	2.96 (2)	C10···C12ⁱⁱ	3.4871 (18)
Cl2···H9ⁱⁱ	3.044 (16)	C14···C20^iv	3.572 (2)
Cl2···H4^iv	3.138 (18)	C5···H16A	2.563 (16)
S1···Cl2^v	3.5832 (5)	C6···H22	2.904 (15)
S1···Cl2^v	3.5832 (5)	C8···H15	2.929 (18)
S1···N1	3.0801 (11)	C16···H5	2.556 (18)
S1···C15	3.1625 (14)	C17···H5	2.829 (18)
S1···C13^v	3.6033 (13)	C18···H3^vi	2.998 (17)
S1···H15	2.578 (18)	C21···H12ⁱ	2.845 (18)
O1···C17	3.2096 (16)	H14···C20^iv	2.964 (18)
O1···C4^vi	3.3346 (17)	H14···C21^iv	2.899 (18)
O1···H9	2.406 (16)	H14···C22^iv	2.990 (18)
O1···H16B	2.345 (16)	H15···C19^iv	2.951 (18)
O1···H4^vi	2.51 (2)	H16B···S1^v	2.852 (16)
N1···S1	3.0801 (11)	H16B···C1^v	2.973 (16)
N1···H22	2.552 (15)	H18···C6^v	2.934 (19)
C1···C12^v	3.4639 (18)	H5···H16A	2.16 (2)
C1···C13^v	3.4372 (18)	H12···H21ⁱ	2.46 (3)
C2···C12^v	3.541 (2)	H15···H21^viii	2.51 (3)
C3···C3^vii	3.485 (2)	H16B···H18	2.51 (2)
C5···C22	3.4988 (19)	H18···H22^v	2.53 (2)
C5···C17	3.4201 (18)

C8—S1—C1	100.14 (6)	C11—C12—C13	118.49 (12)
C7—N1—C6	125.51 (10)	C11—C12—H12	120.1 (11)
C7—N1—C16	115.14 (10)	C13—C12—H12	121.4 (11)
C6—N1—C16	119.20 (10)	C14—C13—C12	121.49 (12)
C2—C1—C6	120.71 (12)	C14—C13—Cl2	119.70 (10)
C2—C1—S1	117.26 (10)	C12—C13—Cl2	118.79 (10)
C6—C1—S1	122.02 (10)	C13—C14—C15	118.94 (12)
C3—C2—C1	120.17 (13)	C13—C14—H14	120.9 (10)
C3—C2—H2	121.4 (10)	C15—C14—H14	120.1 (10)
C1—C2—H2	118.5 (10)	C14—C15—C10	122.24 (12)
C4—C3—C2	119.47 (13)	C14—C15—H15	118.7 (12)
C4—C3—H3	120.7 (10)	C10—C15—H15	118.9 (12)
C2—C3—H3	119.8 (10)	N1—C16—C17	115.04 (10)
C3—C4—C5	120.59 (13)	N1—C16—H16A	107.3 (9)
C3—C4—H4	119.6 (12)	C17—C16—H16A	111.3 (9)
C5—C4—H4	119.7 (12)	N1—C16—H16B	108.1 (10)
C4—C5—C6	120.71 (13)	C17—C16—H16B	109.4 (10)
C4—C5—H5	118.7 (10)	H16A—C16—H16B	105.2 (13)
C6—C5—H5	120.6 (11)	C22—C17—C18	118.42 (12)
C5—C6—C1	118.24 (12)	C22—C17—C16	123.41 (11)
C5—C6—N1	120.50 (11)	C18—C17—C16	118.16 (12)
C1—C6—N1	121.26 (11)	C19—C18—C17	120.85 (14)
O1—C7—N1	120.68 (11)	C19—C18—H18	120.7 (11)
O1—C7—C8	120.54 (11)	C17—C18—H18	118.5 (11)
N1—C7—C8	118.78 (10)	C20—C19—C18	120.29 (14)
C9—C8—C7	117.09 (11)	C20—C19—H19	119.3 (12)
C9—C8—S1	124.79 (10)	C18—C19—H19	120.4 (12)
C7—C8—S1	117.88 (9)	C21—C20—C19	119.32 (14)
C8—C9—C10	129.48 (12)	C21—C20—H20	120.6 (11)
C8—C9—H9	114.8 (10)	C19—C20—H20	120.1 (11)
C10—C9—H9	115.7 (10)	C20—C21—C22	120.69 (14)
C15—C10—C11	116.15 (11)	C20—C21—H21	119.2 (11)
C15—C10—C9	123.53 (12)	C22—C21—H21	120.1 (11)
C11—C10—C9	120.29 (11)	C17—C22—C21	120.43 (13)
C12—C11—C10	122.68 (12)	C17—C22—H22	118.7 (9)
C12—C11—Cl1	117.23 (10)	C21—C22—H22	120.9 (9)
C10—C11—Cl1	120.08 (10)

C8—S1—C1—C2	155.71 (10)	S1—C8—C9—C10	4.6 (2)
C8—S1—C1—C6	−25.73 (11)	C8—C9—C10—C15	−29.8 (2)
C6—C1—C2—C3	−1.12 (19)	C8—C9—C10—C11	152.34 (13)
S1—C1—C2—C3	177.47 (10)	C15—C10—C11—C12	0.42 (18)
C1—C2—C3—C4	3.0 (2)	C9—C10—C11—C12	178.46 (11)
C2—C3—C4—C5	−1.7 (2)	C15—C10—C11—Cl1	179.25 (9)
C3—C4—C5—C6	−1.5 (2)	C9—C10—C11—Cl1	−2.71 (16)
C4—C5—C6—C1	3.35 (19)	C10—C11—C12—C13	−0.78 (19)
C4—C5—C6—N1	−175.72 (12)	Cl1—C11—C12—C13	−179.64 (9)
C2—C1—C6—C5	−2.05 (18)	C11—C12—C13—C14	0.72 (19)
S1—C1—C6—C5	179.43 (9)	C11—C12—C13—Cl2	−177.88 (9)
C2—C1—C6—N1	177.02 (11)	C12—C13—C14—C15	−0.33 (19)
S1—C1—C6—N1	−1.50 (17)	Cl2—C13—C14—C15	178.27 (10)
C7—N1—C6—C5	−158.93 (12)	C13—C14—C15—C10	0.0 (2)
C16—N1—C6—C5	16.29 (17)	C11—C10—C15—C14	0.00 (19)
C7—N1—C6—C1	22.03 (18)	C9—C10—C15—C14	−177.97 (12)
C16—N1—C6—C1	−162.76 (11)	C7—N1—C16—C17	84.01 (14)
C6—N1—C7—O1	174.42 (12)	C6—N1—C16—C17	−91.69 (14)
C16—N1—C7—O1	−0.96 (17)	N1—C16—C17—C22	9.68 (18)
C6—N1—C7—C8	−5.15 (18)	N1—C16—C17—C18	−169.73 (11)
C16—N1—C7—C8	179.46 (10)	C22—C17—C18—C19	0.7 (2)
O1—C7—C8—C9	−23.67 (18)	C16—C17—C18—C19	−179.87 (13)
N1—C7—C8—C9	155.91 (11)	C17—C18—C19—C20	0.1 (2)
O1—C7—C8—S1	150.91 (10)	C18—C19—C20—C21	−0.4 (2)
N1—C7—C8—S1	−29.52 (15)	C19—C20—C21—C22	0.1 (2)
C1—S1—C8—C9	−145.73 (11)	C18—C17—C22—C21	−1.06 (19)
C1—S1—C8—C7	40.15 (10)	C16—C17—C22—C21	179.53 (12)
C7—C8—C9—C10	178.71 (12)	C20—C21—C22—C17	0.7 (2)

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x, −y+1, −z+1; (iii) x−1, y, z+1; (iv) x−1, −y+1/2, z+1/2; (v) x, −y+1/2, z−1/2; (vi) −x+1, y+1/2, −z+1/2; (vii) −x+1, −y, −z+1; (viii) x−1, y, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4···O1^ix	0.936 (19)	2.51 (2)	3.3346 (17)	147.7 (15)
C16—H16B···S1^v	0.945 (16)	2.852 (16)	3.7011 (13)	149.9 (12)
C3—H3···Cg4^ix	0.938 (17)	2.901 (17)	3.6428 (15)	136.8 (13)
C14—H14···Cg4^x	0.971 (19)	2.710 (18)	3.5593 (15)	146.8 (14)
C18—H18···Cg1^xi	0.979 (18)	2.969 (18)	3.6759 (16)	130.0 (13)

Symmetry codes: (v) x, −y+1/2, z−1/2; (ix) −x+1, y−1/2, −z+1/2; (x) x−1, −y−1/2, z−1/2; (xi) x, −y−1/2, z−3/2.

Table 4. Comparison of the selected (X-ray and DFT) geometric data (Å, °) top

Bonds/angles	X-ray	B3LYP/6-311G(d,p)
Cl1—C11	1.7357 (13)	1.80981
Cl2—C13	1.7382 (13)	1.80489
S1—C8	1.7525 (12)	1.80120
S1—C1	1.7561 (13)	1.82629
O1—C7	1.2228 (16)	1.23968
N1—C7	1.3759 (16)	1.38157
N1—C6	1.4192 (16)	1.41776
N1—C16	1.4661 (16)	1.47048
C8—S1—C1	100.14 (6)	98.69028
C7—N1—C6	125.51 (10)	124.58623
C7—N1—C16	115.14 (10)	116.12685
C6—N1—C16	119.20 (10)	119.26679
C2—C1—C6	120.71 (12)	121.24260
C2—C1—S1	117.26 (10)	117.48822
C6—C1—S1	122.02 (10)	121.26667

Table 5. Calculated energies. top

Molecular Energy (a.u.) (eV)	Compound (I)
Total Energy TE (eV)	-62249, 6662
E_HOMO (eV)	-8.2479
E_LUMO (eV)	-2.9115
Gap ΔE (eV)	5.3364
Dipole moment, µ (Debye)	3.4723
Ionisation potential, I (eV)	8.2479
Electron affinity, A	2.9115
Electro negativity, χ	5.3364
Hardness, η	2.6682
Electrophilicity index, ω	5.8340
Softness, σ	0.3748
Fraction of electron transferred, ΔN	0.2662

Acknowledgements

The support of NSF-MRI for the purchase of the diffractometer and Tulane University for support of the Tulane Crystallography Laboratory are gratefully acknowledged.

Funding information

Funding for this research was provided by: NSF-MRI (grant No. 1228232); Hacettepe University Scientific Research Project Unit (grant No. 013 D04 602 004 to TH).

References

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