(Z)-4-n-Butyl-2-(4-chloro­benzyl­idene)-2H-1,4-benzo­thia­zin-3(4H)-one

Ellouz, M.; Sebbar, N.K.; Ouzidan, Y.; Kaur, M.; Essassi, E.M.; Jasinski, J.P.

doi:10.1107/S2414314617008707

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 2| Part 6| June 2017| x170870

https://doi.org/10.1107/S2414314617008707

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(Z)-4-n-Butyl-2-(4-chlorobenzylidene)-2H-1,4-benzothiazin-3(4H)-one

Mohamed Ellouz,^a Nada Kheira Sebbar,^a ^* Younes Ouzidan,^b Manpreet Kaur,^c El Mokhtar Essassi ^a and Jerry P. Jasinski ^c

^aLaboratoire de Chimie Organique Hétérocyclique URAC 21, Pôle de Compétence Pharmacochimie, Av. Ibn Battouta, BP 1014, Faculté des Sciences, Université Mohammed V, Rabat, Morocco, ^bLaboratoire de Chimie Organique Appliquée, Faculté des Sciences et, Techniques, Université Sidi Mohammed Ben Abdellah, Fès, Morocco, and ^cDepartment of Chemistry, Keene State College, 229 Main Street, Keene, NH 03435-2001, USA
^*Correspondence e-mail: nadouchsebbarkheira@gmail.com

Edited by J. Simpson, University of Otago, New Zealand (Received 7 June 2017; accepted 12 June 2017; online 20 June 2017)

In the title compound, C₁₉H₁₈ClNOS, the thiazin-3-one ring adopts a slightly distorted screw-boat conformation. An intramolecular C—H⋯S hydrogen bond encloses an S(6) ring and affects the overall conformation of the molecule. The dihedral angle between the two phenyl rings is 52.3 (2)°. In the crystal, weak C—H⋯O intermolecular interactions stabilize the crystal packing.

Keywords: crystal structure; benzothiazine; hydrogen bonds.

CCDC reference: 1555441

Structure description

1,4-Benzothiazine-containing compounds are important due to their potential applications in the treatment of diabetes complications, by inhibiting aldose reductase (Aotsuka et al., 1994 ). They are also used as analgesics (Wammack et al., 2002 ), Ca²⁺ antagonists (Fujimura et al., 1996 ), and have antimicrobial properties (Zia-ur-Rehman et al., 2009 ). As a continuation of our previous work on the synthesis of new 1,4-benzothiazine derivatives (Sebbar et al.,2016a ,b ; Ellouz et al.,2017a ,b ), we report here the synthesis and crystal structure of the title compound (Fig. 1). This was prepared by reacting (Z)-2-(4-chlorobenzylidene)-2H-1,4-benzothiazin-3(4H)-one with 1-bromobutane, under phase-transfer catalysis conditions using tetra-n-butyl ammonium bromide (TBAB) as a catalyst and potassium carbonate as the base.

Figure 1
Structure of the title compound, showing the atom-numbering scheme, with displacement ellipsoids drawn at the 30% probability level.

The title compound crystallizes with one independent molecule in the asymmetric unit (Fig. 1). The thiazine-3-one ring of the [1,4]thiazin-3-one moiety adopts a slightly distorted screw-boat conformation [puckering parameters: Q = 0.468 (7) Å, θ = 69.8 (7)° and φ = 25.949 (3)°]. An intramolecular C15—H15⋯S1 hydrogen bond forms an S(6) ring motif, and at least partially determines the conformation of the molecule. The dihedral angle between the phenyl rings is 52.3 (2)°.

In the crystal, weak C—H⋯O hydrogen bonds involving O1 as the acceptor, Table 1, link the molecules into a two-dimensional network (Fig. 2).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C6—H6⋯O1ⁱ	0.93	2.53	3.410 (3)	158
C11—H11⋯O1ⁱⁱ	0.93	2.39	3.290 (3)	162
C15—H15⋯S1	0.93	2.55	3.219 (3)	129
Symmetry codes: (i) x, y-1, z; (ii) -x+1, -y+2, -z+1.

Figure 2
The molecular packing of the title compound, viewed along the a axis. Dashed lines indicate weak intra- and intermolecular hydrogen bonds. H atoms not involved in packing have been omitted for clarity.

Synthesis and crystallization

To a solution of (Z)-2-(4-chlorobenzylidene)-2H-1,4-benzothiazin-3(4H)-one (0.49 g,1.5mmol), potassium carbonate (0.41 g,3 mmol) and tetra-n-butyl ammonium bromide (0.048 g,0.15 mmol) in DMF (18 ml) was added 1-bromobutane (3 mmol). Stirring was continued at room temperature for 24 h. The mixture was filtered and the solvent removed. The residue was then washed with water. The organic compound obtained was chromatographed on a column of silica gel with ethyl acetate–hexane (9/1) as the eluent. Colorless prismatic crystals were isolated when the solvent was allowed to evaporate (yield = 51%).

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₉H₁₈ClNOS
M_r	343.85
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	293
a, b, c (Å)	8.8898 (8), 8.9885 (9), 12.1973 (10)
α, β, γ (°)	89.908 (8), 84.490 (7), 63.534 (9)
V (Å³)	867.53 (15)
Z	2
Radiation type	Cu Kα
μ (mm⁻¹)	3.09
Crystal size (mm)	0.34 × 0.32 × 0.14

Data collection
Diffractometer	Rigaku Oxford Diffraction
Absorption correction	Multi-scan (CrysAlis PRO; Rigaku Oxford Diffraction, 2015 $[Rigaku Oxford Diffraction (2015). CrysAlis PRO. Rigaku Americas, The Woodlands, Texas, USA.]$ )
T_min, T_max	0.382, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	5496, 3279, 2807
R_int	0.021
(sin θ/λ)_max (Å⁻¹)	0.615

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.049, 0.146, 1.03
No. of reflections	3279
No. of parameters	210
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.30, −0.32
Computer programs: CrysAlis PRO (Rigaku Oxford Diffraction, 2015 $[Rigaku Oxford Diffraction (2015). CrysAlis PRO. Rigaku Americas, The Woodlands, Texas, USA.]$ ), SHELXT (Sheldrick, 2015a ), SHELXL2014 (Sheldrick, 2015b ) and OLEX2 (Dolomanov et al., 2009 ).

Structural data

CCDC reference: 1555441

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314617008707/sj4118sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314617008707/sj4118Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314617008707/sj4118Isup3.cdx

Supporting information file. DOI: https://doi.org/10.1107/S2414314617008707/sj4118Isup4.cml

checkCIF report

Computing details top

Data collection: CrysAlis PRO (Rigaku Oxford Diffraction, 2015); cell refinement: CrysAlis PRO (Rigaku Oxford Diffraction, 2015); data reduction: CrysAlis PRO (Rigaku Oxford Diffraction, 2015); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

(Z)-4-n-Butyl-2-(4-chlorobenzylidene)-2H-1,4-benzothiazin-3(4H)-one top

Crystal data top

C₁₉H₁₈ClNOS	Z = 2
M_r = 343.85	F(000) = 360
Triclinic, P1	D_x = 1.316 Mg m⁻³
a = 8.8898 (8) Å	Cu Kα radiation, λ = 1.54184 Å
b = 8.9885 (9) Å	Cell parameters from 2206 reflections
c = 12.1973 (10) Å	θ = 5.5–70.9°
α = 89.908 (8)°	µ = 3.09 mm⁻¹
β = 84.490 (7)°	T = 293 K
γ = 63.534 (9)°	Prism, colourless
V = 867.53 (15) Å³	0.34 × 0.32 × 0.14 mm

Data collection top

Rigaku Oxford Diffraction diffractometer	3279 independent reflections
Radiation source: fine-focus sealed X-ray tube, Enhance (Cu) X-ray Source	2807 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.021
Detector resolution: 16.0416 pixels mm^-1	θ_max = 71.5°, θ_min = 3.6°
ω scans	h = −10→10
Absorption correction: multi-scan (CrysAlis PRO; Rigaku Oxford Diffraction, 2015)	k = −11→10
T_min = 0.382, T_max = 1.000	l = −14→14
5496 measured reflections

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.049	w = 1/[σ²(F_o²) + (0.0787P)² + 0.2112P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.146	(Δ/σ)_max < 0.001
S = 1.03	Δρ_max = 0.30 e Å⁻³
3279 reflections	Δρ_min = −0.32 e Å⁻³
210 parameters	Extinction correction: SHELXL2014 (Sheldrick, 2015b), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.0051 (9)
Primary atom site location: dual

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.

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

	x	y	z	U_iso*/U_eq
Cl1	0.09239 (15)	1.18172 (14)	−0.02253 (9)	0.1305 (5)
S1	0.73755 (8)	0.52007 (7)	0.23423 (4)	0.0561 (2)
O1	0.7170 (2)	0.7404 (2)	0.50943 (14)	0.0629 (5)
N1	0.7797 (2)	0.4711 (2)	0.47968 (14)	0.0461 (4)
C1	0.7158 (3)	0.6329 (3)	0.44911 (17)	0.0467 (5)
C2	0.6464 (3)	0.6753 (3)	0.34053 (17)	0.0447 (4)
C3	0.7545 (3)	0.3470 (3)	0.30826 (19)	0.0502 (5)
C4	0.7543 (3)	0.2137 (3)	0.2500 (2)	0.0667 (7)
H4	0.7439	0.2195	0.1747	0.080*
C5	0.7696 (4)	0.0737 (4)	0.3035 (3)	0.0785 (8)
H5	0.7724	−0.0163	0.2643	0.094*
C6	0.7806 (4)	0.0673 (3)	0.4149 (3)	0.0784 (8)
H6	0.7886	−0.0266	0.4513	0.094*
C7	0.7800 (3)	0.1990 (3)	0.4738 (2)	0.0644 (6)
H7	0.7868	0.1934	0.5494	0.077*
C8	0.7693 (3)	0.3403 (3)	0.42042 (18)	0.0470 (5)
C9	0.5312 (3)	0.8316 (3)	0.32848 (17)	0.0487 (5)
H9	0.5091	0.9029	0.3895	0.058*
C10	0.4338 (3)	0.9109 (3)	0.23699 (18)	0.0505 (5)
C11	0.2955 (4)	1.0643 (3)	0.2594 (2)	0.0692 (7)
H11	0.2722	1.1131	0.3301	0.083*
C12	0.1918 (4)	1.1465 (4)	0.1810 (3)	0.0783 (8)
H12	0.0998	1.2496	0.1985	0.094*
C13	0.2237 (4)	1.0772 (4)	0.0775 (3)	0.0783 (8)
C14	0.3614 (6)	0.9286 (4)	0.0506 (3)	0.1164 (16)
H14	0.3849	0.8826	−0.0209	0.140*
C15	0.4653 (5)	0.8471 (4)	0.1298 (2)	0.0944 (12)
H15	0.5595	0.7462	0.1106	0.113*
C16	0.8499 (3)	0.4380 (3)	0.58673 (17)	0.0513 (5)
H16A	0.9118	0.5024	0.5944	0.062*
H16B	0.9298	0.3213	0.5868	0.062*
C17	0.7187 (3)	0.4791 (3)	0.68574 (19)	0.0560 (6)
H17A	0.6484	0.4242	0.6754	0.067*
H17B	0.6467	0.5981	0.6918	0.067*
C18	0.8018 (4)	0.4236 (4)	0.7914 (2)	0.0733 (8)
H18A	0.8518	0.3032	0.7922	0.088*
H18B	0.8921	0.4561	0.7923	0.088*
C19	0.6794 (5)	0.4967 (5)	0.8941 (2)	0.1002 (12)
H19A	0.5910	0.4630	0.8945	0.150*
H19B	0.6314	0.6159	0.8947	0.150*
H19C	0.7382	0.4577	0.9582	0.150*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.1339 (9)	0.1157 (8)	0.0988 (7)	−0.0060 (6)	−0.0706 (7)	0.0190 (6)
S1	0.0688 (4)	0.0496 (3)	0.0409 (3)	−0.0181 (3)	−0.0068 (2)	0.0018 (2)
O1	0.0915 (12)	0.0568 (10)	0.0514 (9)	−0.0403 (9)	−0.0224 (8)	0.0055 (7)
N1	0.0508 (9)	0.0494 (10)	0.0414 (9)	−0.0247 (8)	−0.0084 (7)	0.0074 (7)
C1	0.0537 (11)	0.0504 (11)	0.0423 (10)	−0.0286 (9)	−0.0069 (8)	0.0036 (9)
C2	0.0519 (11)	0.0448 (11)	0.0418 (10)	−0.0253 (9)	−0.0057 (8)	0.0028 (8)
C3	0.0483 (11)	0.0447 (11)	0.0558 (12)	−0.0189 (9)	−0.0062 (9)	0.0007 (9)
C4	0.0734 (16)	0.0558 (14)	0.0703 (16)	−0.0281 (12)	−0.0084 (13)	−0.0105 (12)
C5	0.089 (2)	0.0566 (15)	0.094 (2)	−0.0385 (14)	0.0012 (16)	−0.0144 (15)
C6	0.0883 (19)	0.0477 (14)	0.101 (2)	−0.0353 (13)	0.0089 (16)	0.0044 (14)
C7	0.0722 (15)	0.0531 (13)	0.0659 (15)	−0.0282 (12)	0.0025 (12)	0.0074 (11)
C8	0.0428 (10)	0.0425 (11)	0.0544 (12)	−0.0185 (8)	−0.0017 (8)	0.0026 (9)
C9	0.0598 (12)	0.0453 (11)	0.0436 (11)	−0.0254 (9)	−0.0068 (9)	0.0006 (8)
C10	0.0579 (12)	0.0445 (11)	0.0482 (11)	−0.0215 (9)	−0.0089 (9)	0.0025 (9)
C11	0.0773 (16)	0.0573 (14)	0.0561 (14)	−0.0139 (12)	−0.0132 (12)	−0.0074 (11)
C12	0.0662 (16)	0.0634 (16)	0.0769 (18)	−0.0019 (13)	−0.0160 (14)	0.0033 (14)
C13	0.0865 (19)	0.0689 (17)	0.0680 (17)	−0.0186 (14)	−0.0388 (15)	0.0127 (13)
C14	0.154 (3)	0.073 (2)	0.0598 (18)	0.011 (2)	−0.045 (2)	−0.0094 (15)
C15	0.116 (2)	0.0600 (16)	0.0530 (15)	0.0116 (16)	−0.0220 (16)	−0.0036 (12)
C16	0.0461 (11)	0.0623 (13)	0.0461 (11)	−0.0237 (10)	−0.0110 (9)	0.0111 (9)
C17	0.0521 (12)	0.0673 (14)	0.0468 (12)	−0.0246 (10)	−0.0075 (9)	0.0119 (10)
C18	0.0680 (15)	0.096 (2)	0.0485 (13)	−0.0281 (14)	−0.0131 (11)	0.0150 (13)
C19	0.098 (2)	0.141 (3)	0.0465 (15)	−0.040 (2)	−0.0061 (15)	0.0107 (17)

Geometric parameters (Å, º) top

Cl1—C13	1.740 (3)	C10—C15	1.380 (4)
S1—C2	1.756 (2)	C11—H11	0.9300
S1—C3	1.753 (2)	C11—C12	1.368 (4)
O1—C1	1.220 (3)	C12—H12	0.9300
N1—C1	1.371 (3)	C12—C13	1.355 (4)
N1—C8	1.424 (3)	C13—C14	1.363 (4)
N1—C16	1.474 (3)	C14—H14	0.9300
C1—C2	1.492 (3)	C14—C15	1.374 (4)
C2—C9	1.337 (3)	C15—H15	0.9300
C3—C4	1.395 (3)	C16—H16A	0.9700
C3—C8	1.386 (3)	C16—H16B	0.9700
C4—H4	0.9300	C16—C17	1.517 (3)
C4—C5	1.375 (4)	C17—H17A	0.9700
C5—H5	0.9300	C17—H17B	0.9700
C5—C6	1.371 (5)	C17—C18	1.519 (3)
C6—H6	0.9300	C18—H18A	0.9700
C6—C7	1.384 (4)	C18—H18B	0.9700
C7—H7	0.9300	C18—C19	1.512 (4)
C7—C8	1.395 (3)	C19—H19A	0.9600
C9—H9	0.9300	C19—H19B	0.9600
C9—C10	1.462 (3)	C19—H19C	0.9600
C10—C11	1.383 (3)

C3—S1—C2	99.73 (10)	C11—C12—H12	120.1
C1—N1—C8	124.60 (18)	C13—C12—C11	119.8 (3)
C1—N1—C16	115.97 (17)	C13—C12—H12	120.1
C8—N1—C16	119.20 (17)	C12—C13—Cl1	119.9 (2)
O1—C1—N1	120.5 (2)	C12—C13—C14	120.3 (3)
O1—C1—C2	120.45 (19)	C14—C13—Cl1	119.9 (2)
N1—C1—C2	119.09 (18)	C13—C14—H14	120.2
C1—C2—S1	116.82 (15)	C13—C14—C15	119.6 (3)
C9—C2—S1	124.85 (17)	C15—C14—H14	120.2
C9—C2—C1	118.04 (19)	C10—C15—H15	119.1
C4—C3—S1	117.58 (19)	C14—C15—C10	121.9 (3)
C8—C3—S1	121.84 (17)	C14—C15—H15	119.1
C8—C3—C4	120.6 (2)	N1—C16—H16A	108.7
C3—C4—H4	119.9	N1—C16—H16B	108.7
C5—C4—C3	120.1 (3)	N1—C16—C17	114.37 (17)
C5—C4—H4	119.9	H16A—C16—H16B	107.6
C4—C5—H5	120.1	C17—C16—H16A	108.7
C6—C5—C4	119.8 (3)	C17—C16—H16B	108.7
C6—C5—H5	120.1	C16—C17—H17A	109.4
C5—C6—H6	119.7	C16—C17—H17B	109.4
C5—C6—C7	120.7 (3)	C16—C17—C18	111.19 (19)
C7—C6—H6	119.7	H17A—C17—H17B	108.0
C6—C7—H7	119.8	C18—C17—H17A	109.4
C6—C7—C8	120.4 (3)	C18—C17—H17B	109.4
C8—C7—H7	119.8	C17—C18—H18A	109.0
C3—C8—N1	121.16 (19)	C17—C18—H18B	109.0
C3—C8—C7	118.4 (2)	H18A—C18—H18B	107.8
C7—C8—N1	120.4 (2)	C19—C18—C17	112.9 (2)
C2—C9—H9	114.1	C19—C18—H18A	109.0
C2—C9—C10	131.8 (2)	C19—C18—H18B	109.0
C10—C9—H9	114.1	C18—C19—H19A	109.5
C11—C10—C9	117.3 (2)	C18—C19—H19B	109.5
C15—C10—C9	126.4 (2)	C18—C19—H19C	109.5
C15—C10—C11	116.4 (2)	H19A—C19—H19B	109.5
C10—C11—H11	119.0	H19A—C19—H19C	109.5
C12—C11—C10	122.1 (2)	H19B—C19—H19C	109.5
C12—C11—H11	119.0

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6···O1ⁱ	0.93	2.53	3.410 (3)	158
C11—H11···O1ⁱⁱ	0.93	2.39	3.290 (3)	162
C15—H15···S1	0.93	2.55	3.219 (3)	129

Symmetry codes: (i) x, y−1, z; (ii) −x+1, −y+2, −z+1.

Acknowledgements

JPJ acknowledges the NSF–MRI program (grant No. CHE-1039027) for funds to purchase the X-ray diffractometer.

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