4-(Prop-2-yn­yl)-2H-1,4-benzo­thia­zin-3(4H)-one

Sebbar, N.K.; Zerzouf, A.; Essassi, E.M.; Saadi, M.; El Ammari, L.

doi:10.1107/S160053681400943X

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 70| Part 6| June 2014| Page o641

doi:10.1107/S160053681400943X

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4-(Prop-2-ynyl)-2H-1,4-benzothiazin-3(4H)-one

Nada Kheira Sebbar,^a ^* Abdelfettah Zerzouf,^b El Mokhtar Essassi,^a Mohamed Saadi ^c and Lahcen El Ammari ^c

^aLaboratoire de Chimie Organique Hétérocyclique URAC 21, Pôle de Compétence Pharmacochimie, Av. Ibn Battouta, BP 1014, Faculté des Sciences, Université Mohammed V-Agdal, Rabat, Morocco, ^bLaboratoire de Chimie Organique et Etudes Physicochimiques, ENS Takaddoum, Rabat, Morocco, and ^cLaboratoire de Chimie du Solide Appliquée, Faculté des Sciences, Université Mohammed V-Agdal, Avenue Ibn Battouta, BP 1014, Rabat, Morocco
^*Correspondence e-mail: nk_sebbar@yahoo.fr

(Received 11 April 2014; accepted 26 April 2014; online 10 May 2014)

In the title compound, C₁₁H₉NOS, the six-membered heterocycle of the benzothiazine fragment exhibits a screw-boat conformation. The benzene ring makes a dihedral angle of 79.4 (1)° with the mean plane through the prop-2-ynyl chain and the ring N atom. In the crystal, molecules are linked by C—H⋯O interactions of the acetylenic C—H group towards the carbonyl O atom of a neighbouring molecule, forming zigzag chains running along the b-axis direction.

CCDC reference: 999603

Related literature

For general background to the synthesis of 1,4-benzothiazines derivatives, see: Sebbar et al. (2014 ); Zerzouf et al. (2001 ). For the pharmacological activity of 1,4-benzothiazine derivatives, see: Trapani et al. (1985 ); Yaltirik et al. (2001 ); Wammack et al. (2002 ). For puckering parameters, see: Cremer & Pople (1975 ).

Experimental

Crystal data

C₁₁H₉NOS
M_r = 203.25
Monoclinic, P 2₁ /n
a = 9.005 (2) Å
b = 10.889 (3) Å
c = 10.341 (3) Å
β = 104.565 (7)°
V = 981.3 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.29 mm⁻¹
T = 296 K
0.39 × 0.34 × 0.28 mm

Data collection

Bruker X8 APEX diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ) T_min = 0.692, T_max = 0.747
9586 measured reflections
2532 independent reflections
2242 reflections with I > 2σ(I)
R_int = 0.025

Refinement

R[F² > 2σ(F²)] = 0.033
wR(F²) = 0.097
S = 1.05
2532 reflections
127 parameters
H-atom parameters constrained
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.26 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C11—H11⋯O1ⁱ	0.93	2.32	3.1937 (19)	157
Symmetry code: (i) $[-x+{\script{5\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT-Plus (Bruker, 2009); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ); software used to prepare material for publication: PLATON (Spek, 2009 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 999603

Crystal structure: contains datablock I. DOI: 10.1107/S160053681400943X/im2453sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681400943X/im2453Isup2.hkl

Supporting information file. DOI: 10.1107/S160053681400943X/im2453Isup3.cml

checkCIF report

Comment top

1,4-Benzothiazine derivatives constitute an important class of heterocyclic compounds which possess a wide range of therapeutic and pharmacological properties. Derivatives of 1,4-benzothiazine are widely used as anti-inflammatory (Trapani et al., 1985) and analgesic (Wammack et al., 2002; Yaltirik et al., 2001) drugs. In our previous work we have reported the synthesis of new 1,4-benzothiazine derivatives for biological activities (Zerzouf et al., 2001; Sebbar et al., 2014). The reactivity of propargyl bromide towards 3-oxo-1,4-benzothiazine under phase-transfer catalysis conditions using tetra n-butyl ammonium bromide (TBAB) as catalyst and potassium carbonate as base, leads to the formation of the title compound in good yields.

The two fused six-membered rings building the molecule of the title compound are linked to a prop-2-ynyl chain as shown in Fig.1. The six-membered heterocycle of the benzothiazine fragment displays a screw boat conformation as indicated by the puckering amplitude Q = 0.6643 (11) Å, and spherical polar angle θ = 66.56 (9)°, with ϕ = 330.45 (11)° (Cremer & Pople, 1975). The benzene ring (C1 to C6) makes a dihedral angle of 79.4 (1)° with the mean plan through the prop-2-ynyl chain and the N1 atom (N1C9C10C11).

In the crystal, molecules are linked together by intermolecular C11–H11···O1 interactions forming zigzag chains running along b direction (see Fig.2 and Table 1).

Related literature top

For general background to the synthesis of 1,4-benzothiazines derivatives, see: Sebbar et al. (2014); Zerzouf et al. (2001). For the pharmacological activity of 1,4-benzothiazine derivatives, see: Trapani et al. (1985); Yaltirik et al. (2001); Wammack et al. (2002). For puckering parameters, see: Cremer & Pople (1975).

Experimental top

To a solution of 3-oxo-1,4-benzothiazine (1.00 g, 6.05 mmol), potassium carbonate (1.52 g,11.3 mmol) and tetra n-butyl ammonium bromide (0.12 g, 0.37 mmol) in DMF (25 ml) was added propargyl bromide (0.5 ml, 6.6 mmol). Stirring was continued at room temperature for 24 h. The mixture was filtered and the solvent removed. The residue was extracted with water. The organic compound was chromatographed on a column of silica gel with ethyl acetate-hexane (1/1) as eluent. Orange crystals were isolated when the solvent was allowed to evaporate (yield: 75%, m.p. 493 K).

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT-Plus (Bruker, 2009); data reduction: SAINT-Plus (Bruker, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: PLATON (Spek, 2009) and publCIF (Westrip, 2010).

Figures top

	Fig. 1. Molecular structure of the title compound with the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are represented as small circles.
	Fig. 2. Projection of the structure along (0 0 1) of the title compound, showing molecules linked through C113–H11···O1 hydrogen bond (dashed lines).

4-(Prop-2-ynyl)-2H-1,4-benzothiazin-3(4H)-one top

Crystal data top

C₁₁H₉NOS	F(000) = 424
M_r = 203.25	D_x = 1.376 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2532 reflections
a = 9.005 (2) Å	θ = 2.7–28.7°
b = 10.889 (3) Å	µ = 0.29 mm⁻¹
c = 10.341 (3) Å	T = 296 K
β = 104.565 (7)°	Block, colourless
V = 981.3 (4) Å³	0.39 × 0.34 × 0.28 mm
Z = 4

Data collection top

Bruker X8 APEX diffractometer	2532 independent reflections
Radiation source: fine-focus sealed tube	2242 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.025
ϕ and ω scans	θ_max = 28.7°, θ_min = 2.7°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −12→12
T_min = 0.692, T_max = 0.747	k = −14→14
9586 measured reflections	l = −13→13

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.033	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.097	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0525P)² + 0.1971P] where P = (F_o² + 2F_c²)/3
2532 reflections	(Δ/σ)_max = 0.001
127 parameters	Δρ_max = 0.29 e Å⁻³
0 restraints	Δρ_min = −0.26 e Å⁻³

Crystal data top

C₁₁H₉NOS	V = 981.3 (4) Å³
M_r = 203.25	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 9.005 (2) Å	µ = 0.29 mm⁻¹
b = 10.889 (3) Å	T = 296 K
c = 10.341 (3) Å	0.39 × 0.34 × 0.28 mm
β = 104.565 (7)°

Data collection top

Bruker X8 APEX diffractometer	2532 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2009)	2242 reflections with I > 2σ(I)
T_min = 0.692, T_max = 0.747	R_int = 0.025
9586 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.033	0 restraints
wR(F²) = 0.097	H-atom parameters constrained
S = 1.05	Δρ_max = 0.29 e Å⁻³
2532 reflections	Δρ_min = −0.26 e Å⁻³
127 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s 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 > σ(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
C1	0.72598 (13)	0.66267 (11)	0.41584 (11)	0.0349 (2)
C2	0.57459 (15)	0.63028 (14)	0.40891 (14)	0.0468 (3)
H2	0.5255	0.6635	0.4699	0.056*
C3	0.49680 (15)	0.54991 (15)	0.31310 (16)	0.0545 (4)
H3	0.3950	0.5302	0.3081	0.065*
C4	0.57071 (16)	0.49879 (14)	0.22443 (16)	0.0523 (3)
H4	0.5185	0.4439	0.1599	0.063*
C5	0.72189 (15)	0.52826 (12)	0.23035 (13)	0.0432 (3)
H5	0.7710	0.4922	0.1709	0.052*
C6	0.80051 (12)	0.61176 (10)	0.32501 (11)	0.0321 (2)
C7	1.05883 (13)	0.68706 (11)	0.43826 (12)	0.0365 (2)
C8	1.00619 (14)	0.69227 (13)	0.56496 (12)	0.0400 (3)
H8A	1.0811	0.7365	0.6327	0.048*
H8B	0.9981	0.6096	0.5974	0.048*
C9	1.00187 (16)	0.64258 (13)	0.20101 (12)	0.0430 (3)
H9A	0.9145	0.6591	0.1264	0.052*
H9B	1.0779	0.7059	0.2021	0.052*
C10	1.06719 (14)	0.52290 (14)	0.18089 (12)	0.0430 (3)
N1	0.95243 (11)	0.64883 (9)	0.32600 (9)	0.0343 (2)
C11	1.12110 (16)	0.42755 (16)	0.16435 (14)	0.0528 (3)
H11	1.1637	0.3522	0.1513	0.063*
O1	1.18902 (11)	0.71561 (11)	0.43539 (11)	0.0552 (3)
S1	0.82271 (4)	0.76777 (3)	0.53643 (3)	0.04266 (12)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0342 (5)	0.0363 (6)	0.0354 (5)	0.0037 (4)	0.0114 (4)	0.0046 (4)
C2	0.0349 (6)	0.0579 (8)	0.0515 (7)	0.0039 (5)	0.0181 (5)	0.0071 (6)
C3	0.0322 (6)	0.0634 (9)	0.0667 (9)	−0.0064 (6)	0.0101 (6)	0.0087 (7)
C4	0.0433 (7)	0.0464 (7)	0.0602 (8)	−0.0078 (6)	−0.0002 (6)	−0.0034 (6)
C5	0.0411 (6)	0.0410 (6)	0.0456 (6)	0.0019 (5)	0.0074 (5)	−0.0055 (5)
C6	0.0299 (5)	0.0317 (5)	0.0350 (5)	0.0015 (4)	0.0086 (4)	0.0038 (4)
C7	0.0342 (5)	0.0343 (6)	0.0421 (6)	−0.0021 (4)	0.0115 (4)	0.0026 (5)
C8	0.0376 (6)	0.0451 (6)	0.0359 (6)	−0.0005 (5)	0.0067 (5)	−0.0010 (5)
C9	0.0458 (7)	0.0512 (7)	0.0373 (6)	0.0020 (5)	0.0202 (5)	0.0070 (5)
C10	0.0364 (6)	0.0614 (8)	0.0346 (6)	0.0008 (5)	0.0155 (5)	−0.0003 (5)
N1	0.0335 (5)	0.0389 (5)	0.0340 (5)	−0.0008 (4)	0.0147 (4)	0.0015 (4)
C11	0.0466 (7)	0.0656 (9)	0.0484 (7)	0.0069 (7)	0.0158 (6)	−0.0085 (7)
O1	0.0370 (5)	0.0686 (7)	0.0619 (6)	−0.0143 (4)	0.0160 (4)	0.0024 (5)
S1	0.0458 (2)	0.04378 (19)	0.04046 (19)	0.00495 (12)	0.01474 (14)	−0.00623 (12)

Geometric parameters (Å, º) top

C1—C2	1.3924 (17)	C7—O1	1.2204 (15)
C1—C6	1.3990 (16)	C7—N1	1.3709 (16)
C1—S1	1.7542 (13)	C7—C8	1.5023 (16)
C2—C3	1.374 (2)	C8—S1	1.8021 (13)
C2—H2	0.9300	C8—H8A	0.9700
C3—C4	1.379 (2)	C8—H8B	0.9700
C3—H3	0.9300	C9—C10	1.4660 (19)
C4—C5	1.385 (2)	C9—N1	1.4707 (14)
C4—H4	0.9300	C9—H9A	0.9700
C5—C6	1.3919 (17)	C9—H9B	0.9700
C5—H5	0.9300	C10—C11	1.177 (2)
C6—N1	1.4239 (14)	C11—H11	0.9300

C2—C1—C6	119.60 (12)	N1—C7—C8	116.32 (10)
C2—C1—S1	120.43 (10)	C7—C8—S1	110.60 (9)
C6—C1—S1	119.97 (9)	C7—C8—H8A	109.5
C3—C2—C1	120.88 (13)	S1—C8—H8A	109.5
C3—C2—H2	119.6	C7—C8—H8B	109.5
C1—C2—H2	119.6	S1—C8—H8B	109.5
C2—C3—C4	119.52 (12)	H8A—C8—H8B	108.1
C2—C3—H3	120.2	C10—C9—N1	112.76 (10)
C4—C3—H3	120.2	C10—C9—H9A	109.0
C3—C4—C5	120.71 (13)	N1—C9—H9A	109.0
C3—C4—H4	119.6	C10—C9—H9B	109.0
C5—C4—H4	119.6	N1—C9—H9B	109.0
C4—C5—C6	120.20 (12)	H9A—C9—H9B	107.8
C4—C5—H5	119.9	C11—C10—C9	179.18 (14)
C6—C5—H5	119.9	C7—N1—C6	123.91 (9)
C5—C6—C1	119.07 (11)	C7—N1—C9	117.17 (10)
C5—C6—N1	120.54 (10)	C6—N1—C9	118.89 (10)
C1—C6—N1	120.34 (10)	C10—C11—H11	180.0
O1—C7—N1	121.86 (11)	C1—S1—C8	95.14 (6)
O1—C7—C8	121.83 (12)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C11—H11···O1ⁱ	0.93	2.32	3.1937 (19)	157

Symmetry code: (i) −x+5/2, y−1/2, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C11—H11···O1ⁱ	0.93	2.32	3.1937 (19)	156.9

Symmetry code: (i) −x+5/2, y−1/2, −z+1/2.

Acknowledgements

The authors thank the Unit of Support for Technical and Scientific Research (UATRS, CNRST) for the X-ray measurements.

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