(Z)-2-Benzyl­idene-3-n-but­oxy-2H-1,4-benzo­thia­zine

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

doi:10.1107/S2414314617008902

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 2| Part 6| June 2017| x170890

https://doi.org/10.1107/S2414314617008902

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(Z)-2-Benzylidene-3-n-butoxy-2H-1,4-benzothiazine

Nada Kheira Sebbar,^a Mohamed Ellouz,^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: ellouz.chimie@gmail.com

Edited by J. Simpson, University of Otago, New Zealand (Received 10 June 2017; accepted 14 June 2017; online 27 June 2017)

In the title compound, C₁₉H₁₉NOS, the thiazin-3-one ring of the 1,4-thiazin-3-one moiety adopts a screw-boat conformation. The dihedral angle between the benzene rings is 31.0 (5)°. An intramolecular C—H⋯S hydrogen bond forms an S(6) ring motif. In the crystal, C—H⋯π(ring) contacts form inversion dimers and weak π–π stacking interactions, with a centroid-to-centroid distance of 3.8766 (2) Å, also occur.

Keywords: crystal structure; benzothiazine; hydrogen bonds; π-stacking.

CCDC reference: 1556121

Structure description

1,4-Benzothiazines and their analogues have been studied extensively in different areas of chemistry particularly as pharmaceuticals (Sebbar et al., 2016a ; Ellouz et al.,2017a ; Malagu et al.,1998 ). With respect to their biological applications, they have been found to have potent anti-inflammatory, (Trapani et al.,1985 ); analgesic (Wammack et al., 2002 ) and anti-oxidant properties (Zia-ur-Rehman et al., 2009 ). Slight changes in the substitution pattern in the benzothiazine nucleus can cause a distinguishable difference in their biological properties (Niewiadomy et al., 2011 ; Gautam et al.,2012 ). As a continuation of our research into the development of new 1,4-benzothiazine derivatives with potential pharmacological applications, we have studied the reaction of 1-bromobutane with (Z)-2-benzylidene-2H-1,4-benzothiazin-3(4H)-one under phase-transfer catalysis conditions using tetra-n-butyl ammonium bromide as a catalyst and potassium carbonate as the base (Sebbar et al., 2016b ; Ellouz et al.,2017b ) to give the title compound (Fig. 1).

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

The thiazine-3-one ring of the [1,4]thiazin-3-one moiety adopts a screw-boat conformation (puckering parameters: Q = 0.176 (8) Å, θ = 66.8 (6)° and φ = 26.989 (1)°. The dihedral angle between the benzene rings is 31.0 (5)°. The intramolecular C11—H11⋯S1 hydrogen bond affects the overall conformation of the molecule.

In the crystal C17—H17A⋯Cg2 contacts, Table 1, form inversion dimers and link adjacent molecules in a head-to-tail fashion. In addition, π–π stacking interactions, [Cg3⋯Cg3ⁱⁱⁱ = 3.8766 (2) Å; Cg3 is the centroid of the C10–C15 phenyl ring; symmetry code: (iii) 1 − x, −y, −z] are observed, Fig. 2.

Table 1
Hydrogen-bond geometry (Å, °)

Cg2 is the centroid of the C3–C8 benzene ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C11—H11⋯S1	0.93	2.51	3.155 (2)	127
C17—H17A⋯Cg2ⁱ	0.97	2.82	3.665 (3)	146
Symmetry code: (i) -x, -y+1, -z+1.

Figure 2
The packing of the title compound, viewed along the a axis. Dashed lines indicate weak intramolecular hydrogen bonds. The C—H⋯π contact is not shown.

Synthesis and crystallization

To a solution of (Z)-2-benzylidene-3,4-dihydro-2H-1,4-benzothiazin-3(4H)-one (1.4 mmol), potassium carbonate (2.8 mmol) and tetra-n-butyl ammonium bromide (0.14 mmol) in DMF (15 ml) was added 1-bromobutane (2.8 mmol). Stirring was continued at room temperature for 24 h. The mixture was filtered and the solvent removed. The residue obtained was washed with water. The organic compound was chromatographed on a column of silica gel with ethyl acetate–hexane (9/1) as eluent. Colorless crystals were isolated when the solvent was allowed to evaporate (yield = 21%).

Refinement

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

Table 2
Experimental details

Crystal data
Chemical formula	C₁₉H₁₉NOS
M_r	309.41
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	293
a, b, c (Å)	7.7711 (6), 10.9897 (11), 11.4090 (11)
α, β, γ (°)	112.013 (9), 109.259 (8), 98.120 (7)
V (Å³)	812.78 (14)
Z	2
Radiation type	Cu Kα
μ (mm⁻¹)	1.76
Crystal size (mm)	0.38 × 0.18 × 0.08

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	0.611, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	5063, 3070, 2492
R_int	0.021
(sin θ/λ)_max (Å⁻¹)	0.614

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.048, 0.140, 1.05
No. of reflections	3070
No. of parameters	200
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.55, −0.22
Computer programs: CrysAlis PRO (Rigaku Oxford Diffraction, 2015 $[Rigaku Oxford Diffraction (2015). CrysAlis PRO. Rigaku Americas, The Woodlands, Texas, USA.]$ ), SHELXT (Sheldrick, 2015a ), SHELXL2015 (Sheldrick, 2015b ) and OLEX2 (Dolomanov et al., 2009 ).

Structural data

CCDC reference: 1556121

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314617008902/sj4120sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314617008902/sj4120Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314617008902/sj4120Isup3.cdx

Supporting information file. DOI: https://doi.org/10.1107/S2414314617008902/sj4120Isup4.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: SHELXL2015 (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

(Z)-2-Benzylidene-3-n-butoxy-2H-1,4-benzothiazine top

Crystal data top

C₁₉H₁₉NOS	Z = 2
M_r = 309.41	F(000) = 328
Triclinic, P1	D_x = 1.264 Mg m⁻³
a = 7.7711 (6) Å	Cu Kα radiation, λ = 1.54184 Å
b = 10.9897 (11) Å	Cell parameters from 1693 reflections
c = 11.4090 (11) Å	θ = 7.7–71.5°
α = 112.013 (9)°	µ = 1.76 mm⁻¹
β = 109.259 (8)°	T = 293 K
γ = 98.120 (7)°	Irregular fragment, colourless
V = 812.78 (14) Å³	0.38 × 0.18 × 0.08 mm

Data collection top

Rigaku Oxford Diffraction diffractometer	3070 independent reflections
Radiation source: fine-focus sealed X-ray tube, Enhance (Cu) X-ray Source	2492 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.021
Detector resolution: 16.0416 pixels mm^-1	θ_max = 71.3°, θ_min = 4.6°
ω scans	h = −7→9
Absorption correction: multi-scan (CrysAlis PRO; Rigaku Oxford Diffraction, 2015)	k = −13→12
T_min = 0.611, T_max = 1.000	l = −13→13
5063 measured reflections

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.048	H-atom parameters constrained
wR(F²) = 0.140	w = 1/[σ²(F_o²) + (0.0803P)² + 0.0842P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max < 0.001
3070 reflections	Δρ_max = 0.55 e Å⁻³
200 parameters	Δρ_min = −0.22 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.

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

	x	y	z	U_iso*/U_eq
S1	0.32522 (9)	0.77222 (5)	0.86052 (5)	0.0565 (2)
O1	0.2602 (2)	0.41659 (14)	0.56207 (14)	0.0475 (4)
N1	0.2472 (2)	0.61507 (17)	0.54627 (17)	0.0448 (4)
C1	0.2587 (3)	0.54831 (19)	0.6176 (2)	0.0413 (4)
C2	0.2732 (3)	0.59454 (19)	0.7611 (2)	0.0406 (4)
C3	0.2779 (3)	0.8341 (2)	0.7357 (2)	0.0451 (5)
C4	0.2788 (3)	0.9705 (2)	0.7798 (2)	0.0544 (5)
H4	0.3011	1.0242	0.8717	0.065*
C5	0.2465 (3)	1.0268 (2)	0.6874 (3)	0.0609 (6)
H5	0.2477	1.1182	0.7170	0.073*
C6	0.2124 (4)	0.9460 (3)	0.5503 (3)	0.0611 (6)
H6	0.1905	0.9832	0.4876	0.073*
C7	0.2110 (3)	0.8105 (2)	0.5071 (2)	0.0530 (5)
H7	0.1870	0.7568	0.4148	0.064*
C8	0.2449 (3)	0.7522 (2)	0.5988 (2)	0.0430 (4)
C9	0.2521 (3)	0.5025 (2)	0.8113 (2)	0.0475 (5)
H9	0.2260	0.4115	0.7483	0.057*
C10	0.2635 (3)	0.5220 (2)	0.9482 (2)	0.0474 (5)
C11	0.3516 (3)	0.6452 (2)	1.0698 (2)	0.0546 (5)
H11	0.4089	0.7238	1.0673	0.065*
C12	0.3555 (4)	0.6529 (3)	1.1942 (3)	0.0641 (6)
H12	0.4148	0.7366	1.2742	0.077*
C13	0.2726 (4)	0.5379 (3)	1.2008 (3)	0.0652 (7)
H13	0.2745	0.5436	1.2847	0.078*
C14	0.1869 (4)	0.4144 (3)	1.0823 (3)	0.0692 (7)
H14	0.1311	0.3362	1.0862	0.083*
C15	0.1830 (4)	0.4058 (3)	0.9572 (3)	0.0599 (6)
H15	0.1259	0.3214	0.8780	0.072*
C16	0.2407 (3)	0.3562 (2)	0.4203 (2)	0.0442 (5)
H16A	0.3462	0.4064	0.4126	0.053*
H16B	0.1220	0.3589	0.3588	0.053*
C17	0.2411 (3)	0.2102 (2)	0.3825 (2)	0.0461 (5)
H17A	0.1413	0.1638	0.3982	0.055*
H17B	0.3627	0.2096	0.4427	0.055*
C18	0.2094 (4)	0.1319 (2)	0.2322 (2)	0.0559 (6)
H18A	0.0884	0.1335	0.1723	0.067*
H18B	0.3098	0.1781	0.2170	0.067*
C19	0.2077 (5)	−0.0158 (3)	0.1920 (3)	0.0771 (8)
H19A	0.1921	−0.0594	0.0973	0.116*
H19B	0.1037	−0.0637	0.2015	0.116*
H19C	0.3263	−0.0182	0.2519	0.116*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0843 (4)	0.0397 (3)	0.0369 (3)	0.0152 (3)	0.0219 (3)	0.0130 (2)
O1	0.0704 (9)	0.0385 (7)	0.0368 (7)	0.0201 (6)	0.0245 (7)	0.0170 (6)
N1	0.0552 (10)	0.0411 (9)	0.0409 (9)	0.0154 (7)	0.0217 (8)	0.0194 (7)
C1	0.0465 (10)	0.0361 (10)	0.0379 (10)	0.0116 (8)	0.0182 (8)	0.0132 (8)
C2	0.0444 (10)	0.0375 (10)	0.0376 (10)	0.0122 (8)	0.0168 (8)	0.0150 (8)
C3	0.0456 (10)	0.0407 (10)	0.0467 (11)	0.0098 (8)	0.0175 (9)	0.0202 (9)
C4	0.0560 (12)	0.0409 (11)	0.0530 (13)	0.0082 (9)	0.0189 (10)	0.0135 (10)
C5	0.0643 (14)	0.0381 (11)	0.0760 (16)	0.0154 (10)	0.0253 (12)	0.0250 (11)
C6	0.0744 (16)	0.0543 (13)	0.0695 (16)	0.0237 (12)	0.0308 (13)	0.0404 (12)
C7	0.0659 (14)	0.0512 (12)	0.0497 (12)	0.0203 (10)	0.0272 (10)	0.0267 (10)
C8	0.0447 (10)	0.0408 (10)	0.0457 (11)	0.0124 (8)	0.0192 (8)	0.0216 (9)
C9	0.0577 (12)	0.0406 (10)	0.0422 (11)	0.0130 (9)	0.0216 (9)	0.0167 (9)
C10	0.0538 (11)	0.0522 (12)	0.0457 (11)	0.0215 (9)	0.0236 (9)	0.0270 (10)
C11	0.0646 (13)	0.0537 (13)	0.0451 (12)	0.0118 (10)	0.0217 (10)	0.0253 (10)
C12	0.0822 (17)	0.0664 (15)	0.0439 (12)	0.0205 (13)	0.0265 (12)	0.0256 (11)
C13	0.0890 (18)	0.0771 (17)	0.0560 (14)	0.0359 (14)	0.0405 (13)	0.0438 (13)
C14	0.0971 (19)	0.0635 (16)	0.0714 (17)	0.0250 (14)	0.0448 (15)	0.0460 (14)
C15	0.0818 (16)	0.0500 (13)	0.0533 (13)	0.0198 (11)	0.0295 (12)	0.0275 (11)
C16	0.0555 (12)	0.0394 (10)	0.0360 (10)	0.0124 (8)	0.0208 (9)	0.0147 (8)
C17	0.0536 (12)	0.0420 (11)	0.0428 (11)	0.0159 (9)	0.0209 (9)	0.0180 (9)
C18	0.0669 (14)	0.0508 (12)	0.0472 (12)	0.0176 (10)	0.0292 (11)	0.0145 (10)
C19	0.099 (2)	0.0533 (15)	0.0715 (18)	0.0264 (14)	0.0441 (16)	0.0118 (13)

Geometric parameters (Å, º) top

S1—C2	1.754 (2)	C11—H11	0.9300
S1—C3	1.754 (2)	C11—C12	1.379 (3)
O1—C1	1.349 (2)	C12—H12	0.9300
O1—C16	1.443 (2)	C12—C13	1.376 (4)
N1—C1	1.275 (3)	C13—H13	0.9300
N1—C8	1.403 (3)	C13—C14	1.374 (4)
C1—C2	1.480 (3)	C14—H14	0.9300
C2—C9	1.352 (3)	C14—C15	1.385 (3)
C3—C4	1.390 (3)	C15—H15	0.9300
C3—C8	1.390 (3)	C16—H16A	0.9700
C4—H4	0.9300	C16—H16B	0.9700
C4—C5	1.384 (3)	C16—C17	1.498 (3)
C5—H5	0.9300	C17—H17A	0.9700
C5—C6	1.387 (4)	C17—H17B	0.9700
C6—H6	0.9300	C17—C18	1.516 (3)
C6—C7	1.380 (3)	C18—H18A	0.9700
C7—H7	0.9300	C18—H18B	0.9700
C7—C8	1.393 (3)	C18—C19	1.509 (3)
C9—H9	0.9300	C19—H19A	0.9600
C9—C10	1.465 (3)	C19—H19B	0.9600
C10—C11	1.389 (3)	C19—H19C	0.9600
C10—C15	1.395 (3)

C3—S1—C2	103.27 (10)	C11—C12—H12	119.7
C1—O1—C16	117.28 (15)	C13—C12—C11	120.5 (2)
C1—N1—C8	122.00 (17)	C13—C12—H12	119.7
O1—C1—C2	111.21 (17)	C12—C13—H13	120.3
N1—C1—O1	119.64 (17)	C14—C13—C12	119.4 (2)
N1—C1—C2	129.15 (18)	C14—C13—H13	120.3
C1—C2—S1	116.55 (14)	C13—C14—H14	119.8
C9—C2—S1	123.02 (16)	C13—C14—C15	120.4 (2)
C9—C2—C1	120.40 (18)	C15—C14—H14	119.8
C4—C3—S1	117.21 (17)	C10—C15—H15	119.5
C4—C3—C8	120.7 (2)	C14—C15—C10	120.9 (2)
C8—C3—S1	122.03 (16)	C14—C15—H15	119.5
C3—C4—H4	119.9	O1—C16—H16A	110.3
C5—C4—C3	120.2 (2)	O1—C16—H16B	110.3
C5—C4—H4	119.9	O1—C16—C17	106.89 (16)
C4—C5—H5	120.2	H16A—C16—H16B	108.6
C4—C5—C6	119.6 (2)	C17—C16—H16A	110.3
C6—C5—H5	120.2	C17—C16—H16B	110.3
C5—C6—H6	120.1	C16—C17—H17A	109.2
C7—C6—C5	119.9 (2)	C16—C17—H17B	109.2
C7—C6—H6	120.1	C16—C17—C18	112.25 (18)
C6—C7—H7	119.3	H17A—C17—H17B	107.9
C6—C7—C8	121.4 (2)	C18—C17—H17A	109.2
C8—C7—H7	119.3	C18—C17—H17B	109.2
C3—C8—N1	124.66 (18)	C17—C18—H18A	109.0
C3—C8—C7	118.15 (19)	C17—C18—H18B	109.0
C7—C8—N1	117.17 (19)	H18A—C18—H18B	107.8
C2—C9—H9	114.6	C19—C18—C17	112.9 (2)
C2—C9—C10	130.9 (2)	C19—C18—H18A	109.0
C10—C9—H9	114.6	C19—C18—H18B	109.0
C11—C10—C9	125.5 (2)	C18—C19—H19A	109.5
C11—C10—C15	117.6 (2)	C18—C19—H19B	109.5
C15—C10—C9	116.9 (2)	C18—C19—H19C	109.5
C10—C11—H11	119.4	H19A—C19—H19B	109.5
C12—C11—C10	121.2 (2)	H19A—C19—H19C	109.5
C12—C11—H11	119.4	H19B—C19—H19C	109.5

Hydrogen-bond geometry (Å, º) top

Cg2 is the centroid of the C3–C8 benzene ring.

D—H···A	D—H	H···A	D···A	D—H···A
C11—H11···S1	0.93	2.51	3.155 (2)	127
C17—H17A···Cg2ⁱ	0.97	2.82	3.665 (3)	146

Symmetry code: (i) −x, −y+1, −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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