(2Z)-2-Benzyl­idene-4-(prop-2-yn-1-yl)-2H-1,4-benzo­thia­zin-3(4H)-one

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

doi:10.1107/S1600536814009179

organic compounds

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Volume 70| Part 5| May 2014| Page o614

doi:10.1107/S1600536814009179

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(2Z)-2-Benzylidene-4-(prop-2-yn-1-yl)-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 22 April 2014; accepted 23 April 2014; online 26 April 2014)

The molecule of the title compound, C₁₈H₁₃NOS, is build up from two fused six-membered rings, with the heterocyclic component linked to a benzylidene group and to a prop-2-yn-1-yl chain. The six-membered heterocycle adopts a distorted screw-boat conformation. The prop-2-yn-1-yl chain is almost perpendicular to the mean plane through benzothiazine as indicated by the C—N—C—C torsion angle of 86.5 (2)°. The dihedral angle between the benzene rings is 47.53 (12)°. There are no specific intermolecular interactions in the crystal packing.

CCDC reference: 999032

Related literature

For the pharmacological activity of benzothiazine derivatives, see: Aotsuka et al. (1994 ); Fujimura et al. (1996 ); Rathore & Kumar (2006 ); Fringuelli et al. (1998 ). For related structures, see: Sebbar et al. (2014a ,b ); Zerzouf et al. (2001 ). For conformation analysis, see: Cremer & Pople (1975 ).

Experimental

Crystal data

C₁₈H₁₃NOS
M_r = 291.35
Orthorhombic, P b c a
a = 9.0254 (13) Å
b = 7.7388 (12) Å
c = 42.488 (7) Å
V = 2967.6 (8) Å³
Z = 8
Mo Kα radiation
μ = 0.22 mm⁻¹
T = 296 K
0.42 × 0.36 × 0.31 mm

Data collection

Bruker X8 APEX diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ) T_min = 0.579, T_max = 0.746
14350 measured reflections
3248 independent reflections
2227 reflections with I > 2σ(I)
R_int = 0.038

Refinement

R[F² > 2σ(F²)] = 0.046
wR(F²) = 0.124
S = 1.02
3248 reflections
190 parameters
H-atom parameters constrained
Δρ_max = 0.24 e Å⁻³
Δρ_min = −0.30 e Å⁻³

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: 999032

Crystal structure: contains datablock I. DOI: 10.1107/S1600536814009179/tk5310sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536814009179/tk5310Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536814009179/tk5310Isup3.cml

checkCIF report

Structural commentary top

Benzothiazine containing compounds are important due to their potential applications as treatment of diabete complications, by inhibiting aldose reductase (Aotsuka et al., 1994), having activities antagonists of Ca²⁺ (Fujimura et al., 1996), antimicrobial and antifungal (Rathore & Kumar, 2006; Fringuelli et al., 1998). The present work is a continuation of the investigation of the benzothiazine derivatives published recently by our team (Sebbar et al., 2014a; 2014b; Zerzouf et al., 2001). In this work, we are interested in the synthesis of the title compound for biological activities, by reacting (2Z)-2-(benzylidene)-3,4-dihydro-2H-1,4- benzothiazin-3-one with propargyl bromide, under phase-transfer catalysis conditions using tetra n-butyl ammonium bromide (TBAB) as catalyst and potassium carbonate as base (Scheme 1).

In the molecule of the title compound, the six-membered heterocycle (S1N1C1C6C7C8) of the benzothiazine fragment exhibits a conformation between boat and screw boat conformation as indicated by the puckering amplitude Q = 0.6536 (17) Å, and spherical polar angle θ = 112.04 (16)°, with ϕ = 152.14 (18)° (Cremer & Pople, 1975). The prop-2-yn-1-yl chain is almost perpendicular to mean plane through the benzene ring, as indicated by the torsion angle C6–N1–C16–C17 of 86.5 (2)° (Fig. 1). The dihedral angle between the two planes through the benzene rings (C1 to C6 and C10 to C15) is of 47.53 (12)°.

Synthesis and crystallization top

To a mixture of (2Z)-2-(benzylidene)-3,4-dihydro-2H-1,4-benzothiazin-3-one (0.38 g, 1.5 mmol), potassium carbonate (0.24 g, 1.8 mmol) and tetra n-butyl ammonium bromide (0.05 g, 0.15 mmol) in DMF (25 ml) was added propargyl bromide (0.12 ml, 1.6 mmol). Stirring was continued at room temperature for 24 h. The salt was removed by filtration and the filtrate was concentrated under reduced pressure. The residue was separated by chromatography on a column of silica gel with ethyl acetate-hexane as eluent; yellow crystals were obtained upon evaporation of the solvent (yield = 55% and m.pt = 404 K).

Refinement top

The H atoms were located in a difference map and treated as riding with C—H = 0.93 Å (aromatic, acetylenic) and C—H = 0.97 Å (methylene), and with U_iso(H) = 1.2 U_eq(C).

Related literature top

For the pharmacological activity of benzothiazine derivatives, see: Aotsuka et al. (1994); Fujimura et al. (1996); Rathore & Kumar (2006); Fringuelli et al. (1998). For related structures, see: Sebbar et al. (2014a,b); Zerzouf et al. (2001). For conformation analysis, see: Cremer & Pople (1975).

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.

(2Z)-2-Benzylidene-4-(prop-2-yn-1-yl)-2H-1,4-benzothiazin-3(4H)-one top

Crystal data top

C₁₈H₁₃NOS	D_x = 1.304 Mg m⁻³
M_r = 291.35	Melting point: 404 K
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 3248 reflections
a = 9.0254 (13) Å	θ = 2.5–27.1°
b = 7.7388 (12) Å	µ = 0.22 mm⁻¹
c = 42.488 (7) Å	T = 296 K
V = 2967.6 (8) Å³	Block, yellow
Z = 8	0.42 × 0.36 × 0.31 mm
F(000) = 1216

Data collection top

Bruker X8 APEX diffractometer	3248 independent reflections
Radiation source: fine-focus sealed tube	2227 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.038
ϕ and ω scans	θ_max = 27.1°, θ_min = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −10→11
T_min = 0.579, T_max = 0.746	k = −5→9
14350 measured reflections	l = −54→42

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)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.124	H-atom parameters constrained
S = 1.02	w = 1/[σ²(F_o²) + (0.0511P)² + 0.8991P] where P = (F_o² + 2F_c²)/3
3248 reflections	(Δ/σ)_max < 0.001
190 parameters	Δρ_max = 0.24 e Å⁻³
0 restraints	Δρ_min = −0.30 e Å⁻³

Crystal data top

C₁₈H₁₃NOS	V = 2967.6 (8) Å³
M_r = 291.35	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 9.0254 (13) Å	µ = 0.22 mm⁻¹
b = 7.7388 (12) Å	T = 296 K
c = 42.488 (7) Å	0.42 × 0.36 × 0.31 mm

Data collection top

Bruker X8 APEX diffractometer	3248 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2009)	2227 reflections with I > 2σ(I)
T_min = 0.579, T_max = 0.746	R_int = 0.038
14350 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.046	0 restraints
wR(F²) = 0.124	H-atom parameters constrained
S = 1.02	Δρ_max = 0.24 e Å⁻³
3248 reflections	Δρ_min = −0.30 e Å⁻³
190 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	0.2609 (2)	0.8787 (2)	0.10840 (5)	0.0479 (5)
C2	0.1083 (2)	0.8810 (3)	0.10322 (6)	0.0565 (6)
H2	0.0443	0.8448	0.1191	0.068*
C3	0.0518 (2)	0.9359 (3)	0.07502 (6)	0.0615 (6)
H3	−0.0501	0.9412	0.0720	0.074*
C4	0.1463 (2)	0.9829 (3)	0.05121 (6)	0.0606 (6)
H4	0.1081	1.0198	0.0320	0.073*
C5	0.2986 (2)	0.9758 (3)	0.05563 (5)	0.0531 (5)
H5	0.3618	1.0037	0.0391	0.064*
C6	0.35728 (19)	0.9276 (2)	0.08436 (5)	0.0438 (5)
C7	0.5877 (2)	0.8372 (3)	0.11202 (5)	0.0476 (5)
C8	0.5034 (2)	0.7547 (3)	0.13808 (5)	0.0479 (5)
C9	0.5746 (2)	0.6372 (3)	0.15553 (5)	0.0552 (5)
H9	0.6729	0.6203	0.1498	0.066*
C10	0.5260 (2)	0.5307 (3)	0.18189 (5)	0.0570 (5)
C11	0.6072 (3)	0.3823 (4)	0.18816 (7)	0.0896 (9)
H11	0.6905	0.3577	0.1761	0.107*
C12	0.5674 (4)	0.2717 (5)	0.21174 (8)	0.1084 (11)
H12	0.6237	0.1730	0.2154	0.130*
C13	0.4463 (3)	0.3036 (4)	0.23001 (7)	0.0863 (8)
H13	0.4196	0.2274	0.2460	0.104*
C14	0.3653 (3)	0.4485 (4)	0.22456 (6)	0.0762 (7)
H14	0.2826	0.4716	0.2369	0.091*
C15	0.4043 (3)	0.5618 (3)	0.20089 (5)	0.0671 (6)
H15	0.3478	0.6608	0.1977	0.081*
C16	0.6078 (2)	1.0153 (3)	0.06611 (5)	0.0508 (5)
H16A	0.5557	1.1143	0.0575	0.061*
H16B	0.6966	1.0574	0.0764	0.061*
C17	0.6504 (2)	0.9004 (3)	0.04036 (5)	0.0532 (5)
C18	0.6844 (3)	0.8080 (4)	0.01999 (6)	0.0761 (7)
H18	0.7116	0.7341	0.0037	0.091*
N1	0.51305 (15)	0.9304 (2)	0.08949 (4)	0.0455 (4)
O1	0.72273 (14)	0.8256 (2)	0.11070 (4)	0.0649 (4)
S1	0.32280 (6)	0.82420 (9)	0.145920 (14)	0.0667 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0428 (9)	0.0399 (10)	0.0610 (13)	0.0036 (8)	0.0089 (9)	−0.0108 (9)
C2	0.0426 (10)	0.0505 (12)	0.0763 (16)	0.0000 (9)	0.0150 (11)	−0.0098 (11)
C3	0.0394 (10)	0.0539 (12)	0.0912 (18)	0.0034 (9)	−0.0007 (11)	−0.0134 (13)
C4	0.0519 (11)	0.0600 (13)	0.0698 (15)	0.0084 (10)	−0.0087 (11)	−0.0048 (12)
C5	0.0457 (10)	0.0527 (12)	0.0610 (14)	−0.0002 (9)	0.0028 (10)	−0.0015 (10)
C6	0.0371 (9)	0.0355 (9)	0.0586 (13)	0.0003 (7)	0.0039 (8)	−0.0079 (9)
C7	0.0424 (10)	0.0479 (11)	0.0525 (12)	−0.0026 (8)	0.0020 (8)	−0.0078 (10)
C8	0.0468 (10)	0.0494 (11)	0.0476 (11)	−0.0006 (9)	0.0022 (9)	−0.0093 (10)
C9	0.0527 (11)	0.0587 (13)	0.0543 (13)	−0.0017 (10)	−0.0018 (10)	−0.0070 (11)
C10	0.0606 (12)	0.0624 (14)	0.0481 (12)	−0.0023 (10)	−0.0088 (10)	−0.0051 (11)
C11	0.0892 (18)	0.100 (2)	0.0790 (19)	0.0273 (16)	0.0084 (15)	0.0242 (17)
C12	0.117 (3)	0.110 (2)	0.098 (2)	0.032 (2)	0.006 (2)	0.045 (2)
C13	0.099 (2)	0.094 (2)	0.0654 (18)	−0.0107 (17)	−0.0083 (16)	0.0213 (16)
C14	0.0838 (16)	0.094 (2)	0.0507 (14)	−0.0108 (15)	0.0001 (13)	−0.0006 (14)
C15	0.0807 (15)	0.0700 (15)	0.0506 (14)	0.0014 (13)	0.0015 (12)	−0.0025 (12)
C16	0.0395 (9)	0.0467 (11)	0.0662 (14)	−0.0037 (8)	0.0062 (9)	0.0011 (10)
C17	0.0492 (11)	0.0534 (12)	0.0569 (14)	0.0037 (9)	0.0078 (10)	0.0095 (11)
C18	0.0952 (18)	0.0717 (17)	0.0614 (16)	0.0160 (14)	0.0134 (14)	0.0044 (14)
N1	0.0373 (7)	0.0437 (9)	0.0555 (10)	−0.0022 (6)	0.0045 (7)	−0.0020 (8)
O1	0.0399 (7)	0.0831 (11)	0.0718 (10)	−0.0003 (7)	0.0004 (7)	0.0077 (9)
S1	0.0603 (3)	0.0835 (4)	0.0565 (4)	0.0174 (3)	0.0176 (3)	0.0016 (3)

Geometric parameters (Å, º) top

C1—C6	1.394 (3)	C9—H9	0.9300
C1—C2	1.394 (3)	C10—C15	1.384 (3)
C1—S1	1.741 (2)	C10—C11	1.388 (3)
C2—C3	1.369 (3)	C11—C12	1.366 (4)
C2—H2	0.9300	C11—H11	0.9300
C3—C4	1.372 (3)	C12—C13	1.363 (4)
C3—H3	0.9300	C12—H12	0.9300
C4—C5	1.389 (3)	C13—C14	1.358 (4)
C4—H4	0.9300	C13—H13	0.9300
C5—C6	1.382 (3)	C14—C15	1.380 (3)
C5—H5	0.9300	C14—H14	0.9300
C6—N1	1.423 (2)	C15—H15	0.9300
C7—O1	1.224 (2)	C16—C17	1.461 (3)
C7—N1	1.375 (2)	C16—N1	1.466 (2)
C7—C8	1.488 (3)	C16—H16A	0.9700
C8—C9	1.338 (3)	C16—H16B	0.9700
C8—S1	1.7482 (19)	C17—C18	1.164 (3)
C9—C10	1.458 (3)	C18—H18	0.9300

C6—C1—C2	119.8 (2)	C11—C10—C9	117.1 (2)
C6—C1—S1	122.42 (15)	C12—C11—C10	121.3 (3)
C2—C1—S1	117.68 (16)	C12—C11—H11	119.3
C3—C2—C1	120.6 (2)	C10—C11—H11	119.3
C3—C2—H2	119.7	C13—C12—C11	121.0 (3)
C1—C2—H2	119.7	C13—C12—H12	119.5
C2—C3—C4	119.73 (19)	C11—C12—H12	119.5
C2—C3—H3	120.1	C14—C13—C12	118.9 (3)
C4—C3—H3	120.1	C14—C13—H13	120.5
C3—C4—C5	120.3 (2)	C12—C13—H13	120.5
C3—C4—H4	119.8	C13—C14—C15	120.8 (3)
C5—C4—H4	119.8	C13—C14—H14	119.6
C6—C5—C4	120.6 (2)	C15—C14—H14	119.6
C6—C5—H5	119.7	C14—C15—C10	121.1 (2)
C4—C5—H5	119.7	C14—C15—H15	119.4
C5—C6—C1	118.78 (17)	C10—C15—H15	119.4
C5—C6—N1	120.64 (17)	C17—C16—N1	112.83 (16)
C1—C6—N1	120.57 (18)	C17—C16—H16A	109.0
O1—C7—N1	119.64 (18)	N1—C16—H16A	109.0
O1—C7—C8	120.80 (19)	C17—C16—H16B	109.0
N1—C7—C8	119.54 (16)	N1—C16—H16B	109.0
C9—C8—C7	117.30 (18)	H16A—C16—H16B	107.8
C9—C8—S1	123.48 (16)	C18—C17—C16	179.5 (2)
C7—C8—S1	119.10 (15)	C17—C18—H18	180.0
C8—C9—C10	131.7 (2)	C7—N1—C6	125.65 (16)
C8—C9—H9	114.1	C7—N1—C16	114.90 (15)
C10—C9—H9	114.1	C6—N1—C16	118.65 (16)
C15—C10—C11	116.8 (2)	C1—S1—C8	101.50 (9)
C15—C10—C9	126.0 (2)

Experimental details

Crystal data
Chemical formula	C₁₈H₁₃NOS
M_r	291.35
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	296
a, b, c (Å)	9.0254 (13), 7.7388 (12), 42.488 (7)
V (Å³)	2967.6 (8)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.22
Crystal size (mm)	0.42 × 0.36 × 0.31

Data collection
Diffractometer	Bruker X8 APEX diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2009)
T_min, T_max	0.579, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	14350, 3248, 2227
R_int	0.038
(sin θ/λ)_max (Å⁻¹)	0.641

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.046, 0.124, 1.02
No. of reflections	3248
No. of parameters	190
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.24, −0.30

Computer programs: APEX2 (Bruker, 2009), SAINT-Plus (Bruker, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 2012), PLATON (Spek, 2009) and publCIF (Westrip, 2010).

Acknowledgements

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

References

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