organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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ISSN: 2056-9890

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

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.

Related literature

For the pharmacological activity of benzo­thia­zine derivatives, see: Aotsuka et al. (1994[Aotsuka, T., Hosono, H., Kurihara, T., Nakamura, Y., Matsui, T. & Kobayashi, F. (1994). Chem. Pharm. Bull. 42, 1264-1271.]); Fujimura et al. (1996[Fujimura, K., Ota, A. & Kawashima, Y. (1996). Chem. Pharm. Bull. 44, 542-546.]); Rathore & Kumar (2006[Rathore, B. S. & Kumar, M. (2006). Bioorg. Med. Chem. 14, 5678-5682.]); Fringuelli et al. (1998[Fringuelli, R., Schiaffella, F., Bistoni, F., Pitzurra, L. & Vecchiarelli, A. (1998). Bioorg. Med. Chem. 6, 103-108.]). For related structures, see: Sebbar et al. (2014a[Sebbar, N. K., Zerzouf, A., Essassi, E. M., Saadi, M. & El Ammari, L. (2014a). Acta Cryst. E70, o160-o161.],b[Sebbar, N. K., Zerzouf, A., Essassi, E. M., Saadi, M. & El Ammari, L. (2014b). Acta Cryst. E70, o116.]); Zerzouf et al. (2001[Zerzouf, A., Salem, M., Essassi, E. M. & Pierrot, M. (2001). Acta Cryst. E57, o498-o499.]). For conformation analysis, see: Cremer & Pople (1975[Cremer, D. & Pople, J. A. (1975). J. Am. Chem. Soc. 97, 1354-1358.]).

[Scheme 1]

Experimental

Crystal data
  • C18H13NOS

  • Mr = 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[Bruker (2009). APEX2, SAINT-Plus and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.579, Tmax = 0.746

  • 14350 measured reflections

  • 3248 independent reflections

  • 2227 reflections with I > 2σ(I)

  • Rint = 0.038

Refinement
  • R[F2 > 2σ(F2)] = 0.046

  • wR(F2) = 0.124

  • S = 1.02

  • 3248 reflections

  • 190 parameters

  • H-atom parameters constrained

  • Δρmax = 0.24 e Å−3

  • Δρmin = −0.30 e Å−3

Data collection: APEX2 (Bruker, 2009[Bruker (2009). APEX2, SAINT-Plus and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT-Plus (Bruker, 2009[Bruker (2009). APEX2, SAINT-Plus and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012[Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849-854.]); software used to prepare material for publication: PLATON (Spek, 2009[Spek, A. L. (2009). Acta Cryst. D65, 148-155.]) and publCIF (Westrip, 2010[Westrip, S. P. (2010). J. Appl. Cryst. 43, 920-925.]).

Supporting information


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 Uiso(H) = 1.2 Ueq(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
[Figure 1] 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
C18H13NOSDx = 1.304 Mg m3
Mr = 291.35Melting point: 404 K
Orthorhombic, PbcaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2abCell parameters from 3248 reflections
a = 9.0254 (13) Åθ = 2.5–27.1°
b = 7.7388 (12) ŵ = 0.22 mm1
c = 42.488 (7) ÅT = 296 K
V = 2967.6 (8) Å3Block, yellow
Z = 80.42 × 0.36 × 0.31 mm
F(000) = 1216
Data collection top
Bruker X8 APEX
diffractometer
3248 independent reflections
Radiation source: fine-focus sealed tube2227 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.038
ϕ and ω scansθmax = 27.1°, θmin = 2.5°
Absorption correction: multi-scan
(SADABS; Bruker, 2009)
h = 1011
Tmin = 0.579, Tmax = 0.746k = 59
14350 measured reflectionsl = 5442
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.046Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.124H-atom parameters constrained
S = 1.02 w = 1/[σ2(Fo2) + (0.0511P)2 + 0.8991P]
where P = (Fo2 + 2Fc2)/3
3248 reflections(Δ/σ)max < 0.001
190 parametersΔρmax = 0.24 e Å3
0 restraintsΔρmin = 0.30 e Å3
Crystal data top
C18H13NOSV = 2967.6 (8) Å3
Mr = 291.35Z = 8
Orthorhombic, PbcaMo Kα radiation
a = 9.0254 (13) ŵ = 0.22 mm1
b = 7.7388 (12) ÅT = 296 K
c = 42.488 (7) Å0.42 × 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)
Tmin = 0.579, Tmax = 0.746Rint = 0.038
14350 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0460 restraints
wR(F2) = 0.124H-atom parameters constrained
S = 1.02Δρmax = 0.24 e Å3
3248 reflectionsΔρmin = 0.30 e Å3
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
xyzUiso*/Ueq
C10.2609 (2)0.8787 (2)0.10840 (5)0.0479 (5)
C20.1083 (2)0.8810 (3)0.10322 (6)0.0565 (6)
H20.04430.84480.11910.068*
C30.0518 (2)0.9359 (3)0.07502 (6)0.0615 (6)
H30.05010.94120.07200.074*
C40.1463 (2)0.9829 (3)0.05121 (6)0.0606 (6)
H40.10811.01980.03200.073*
C50.2986 (2)0.9758 (3)0.05563 (5)0.0531 (5)
H50.36181.00370.03910.064*
C60.35728 (19)0.9276 (2)0.08436 (5)0.0438 (5)
C70.5877 (2)0.8372 (3)0.11202 (5)0.0476 (5)
C80.5034 (2)0.7547 (3)0.13808 (5)0.0479 (5)
C90.5746 (2)0.6372 (3)0.15553 (5)0.0552 (5)
H90.67290.62030.14980.066*
C100.5260 (2)0.5307 (3)0.18189 (5)0.0570 (5)
C110.6072 (3)0.3823 (4)0.18816 (7)0.0896 (9)
H110.69050.35770.17610.107*
C120.5674 (4)0.2717 (5)0.21174 (8)0.1084 (11)
H120.62370.17300.21540.130*
C130.4463 (3)0.3036 (4)0.23001 (7)0.0863 (8)
H130.41960.22740.24600.104*
C140.3653 (3)0.4485 (4)0.22456 (6)0.0762 (7)
H140.28260.47160.23690.091*
C150.4043 (3)0.5618 (3)0.20089 (5)0.0671 (6)
H150.34780.66080.19770.081*
C160.6078 (2)1.0153 (3)0.06611 (5)0.0508 (5)
H16A0.55571.11430.05750.061*
H16B0.69661.05740.07640.061*
C170.6504 (2)0.9004 (3)0.04036 (5)0.0532 (5)
C180.6844 (3)0.8080 (4)0.01999 (6)0.0761 (7)
H180.71160.73410.00370.091*
N10.51305 (15)0.9304 (2)0.08949 (4)0.0455 (4)
O10.72273 (14)0.8256 (2)0.11070 (4)0.0649 (4)
S10.32280 (6)0.82420 (9)0.145920 (14)0.0667 (2)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0428 (9)0.0399 (10)0.0610 (13)0.0036 (8)0.0089 (9)0.0108 (9)
C20.0426 (10)0.0505 (12)0.0763 (16)0.0000 (9)0.0150 (11)0.0098 (11)
C30.0394 (10)0.0539 (12)0.0912 (18)0.0034 (9)0.0007 (11)0.0134 (13)
C40.0519 (11)0.0600 (13)0.0698 (15)0.0084 (10)0.0087 (11)0.0048 (12)
C50.0457 (10)0.0527 (12)0.0610 (14)0.0002 (9)0.0028 (10)0.0015 (10)
C60.0371 (9)0.0355 (9)0.0586 (13)0.0003 (7)0.0039 (8)0.0079 (9)
C70.0424 (10)0.0479 (11)0.0525 (12)0.0026 (8)0.0020 (8)0.0078 (10)
C80.0468 (10)0.0494 (11)0.0476 (11)0.0006 (9)0.0022 (9)0.0093 (10)
C90.0527 (11)0.0587 (13)0.0543 (13)0.0017 (10)0.0018 (10)0.0070 (11)
C100.0606 (12)0.0624 (14)0.0481 (12)0.0023 (10)0.0088 (10)0.0051 (11)
C110.0892 (18)0.100 (2)0.0790 (19)0.0273 (16)0.0084 (15)0.0242 (17)
C120.117 (3)0.110 (2)0.098 (2)0.032 (2)0.006 (2)0.045 (2)
C130.099 (2)0.094 (2)0.0654 (18)0.0107 (17)0.0083 (16)0.0213 (16)
C140.0838 (16)0.094 (2)0.0507 (14)0.0108 (15)0.0001 (13)0.0006 (14)
C150.0807 (15)0.0700 (15)0.0506 (14)0.0014 (13)0.0015 (12)0.0025 (12)
C160.0395 (9)0.0467 (11)0.0662 (14)0.0037 (8)0.0062 (9)0.0011 (10)
C170.0492 (11)0.0534 (12)0.0569 (14)0.0037 (9)0.0078 (10)0.0095 (11)
C180.0952 (18)0.0717 (17)0.0614 (16)0.0160 (14)0.0134 (14)0.0044 (14)
N10.0373 (7)0.0437 (9)0.0555 (10)0.0022 (6)0.0045 (7)0.0020 (8)
O10.0399 (7)0.0831 (11)0.0718 (10)0.0003 (7)0.0004 (7)0.0077 (9)
S10.0603 (3)0.0835 (4)0.0565 (4)0.0174 (3)0.0176 (3)0.0016 (3)
Geometric parameters (Å, º) top
C1—C61.394 (3)C9—H90.9300
C1—C21.394 (3)C10—C151.384 (3)
C1—S11.741 (2)C10—C111.388 (3)
C2—C31.369 (3)C11—C121.366 (4)
C2—H20.9300C11—H110.9300
C3—C41.372 (3)C12—C131.363 (4)
C3—H30.9300C12—H120.9300
C4—C51.389 (3)C13—C141.358 (4)
C4—H40.9300C13—H130.9300
C5—C61.382 (3)C14—C151.380 (3)
C5—H50.9300C14—H140.9300
C6—N11.423 (2)C15—H150.9300
C7—O11.224 (2)C16—C171.461 (3)
C7—N11.375 (2)C16—N11.466 (2)
C7—C81.488 (3)C16—H16A0.9700
C8—C91.338 (3)C16—H16B0.9700
C8—S11.7482 (19)C17—C181.164 (3)
C9—C101.458 (3)C18—H180.9300
C6—C1—C2119.8 (2)C11—C10—C9117.1 (2)
C6—C1—S1122.42 (15)C12—C11—C10121.3 (3)
C2—C1—S1117.68 (16)C12—C11—H11119.3
C3—C2—C1120.6 (2)C10—C11—H11119.3
C3—C2—H2119.7C13—C12—C11121.0 (3)
C1—C2—H2119.7C13—C12—H12119.5
C2—C3—C4119.73 (19)C11—C12—H12119.5
C2—C3—H3120.1C14—C13—C12118.9 (3)
C4—C3—H3120.1C14—C13—H13120.5
C3—C4—C5120.3 (2)C12—C13—H13120.5
C3—C4—H4119.8C13—C14—C15120.8 (3)
C5—C4—H4119.8C13—C14—H14119.6
C6—C5—C4120.6 (2)C15—C14—H14119.6
C6—C5—H5119.7C14—C15—C10121.1 (2)
C4—C5—H5119.7C14—C15—H15119.4
C5—C6—C1118.78 (17)C10—C15—H15119.4
C5—C6—N1120.64 (17)C17—C16—N1112.83 (16)
C1—C6—N1120.57 (18)C17—C16—H16A109.0
O1—C7—N1119.64 (18)N1—C16—H16A109.0
O1—C7—C8120.80 (19)C17—C16—H16B109.0
N1—C7—C8119.54 (16)N1—C16—H16B109.0
C9—C8—C7117.30 (18)H16A—C16—H16B107.8
C9—C8—S1123.48 (16)C18—C17—C16179.5 (2)
C7—C8—S1119.10 (15)C17—C18—H18180.0
C8—C9—C10131.7 (2)C7—N1—C6125.65 (16)
C8—C9—H9114.1C7—N1—C16114.90 (15)
C10—C9—H9114.1C6—N1—C16118.65 (16)
C15—C10—C11116.8 (2)C1—S1—C8101.50 (9)
C15—C10—C9126.0 (2)

Experimental details

Crystal data
Chemical formulaC18H13NOS
Mr291.35
Crystal system, space groupOrthorhombic, Pbca
Temperature (K)296
a, b, c (Å)9.0254 (13), 7.7388 (12), 42.488 (7)
V3)2967.6 (8)
Z8
Radiation typeMo Kα
µ (mm1)0.22
Crystal size (mm)0.42 × 0.36 × 0.31
Data collection
DiffractometerBruker X8 APEX
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 2009)
Tmin, Tmax0.579, 0.746
No. of measured, independent and
observed [I > 2σ(I)] reflections
14350, 3248, 2227
Rint0.038
(sin θ/λ)max1)0.641
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.046, 0.124, 1.02
No. of reflections3248
No. of parameters190
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)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

First citationAotsuka, T., Hosono, H., Kurihara, T., Nakamura, Y., Matsui, T. & Kobayashi, F. (1994). Chem. Pharm. Bull. 42, 1264–1271.  CrossRef CAS PubMed
First citationBruker (2009). APEX2, SAINT-Plus and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.
First citationCremer, D. & Pople, J. A. (1975). J. Am. Chem. Soc. 97, 1354–1358.  CrossRef CAS Web of Science
First citationFarrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854.  Web of Science CrossRef CAS IUCr Journals
First citationFringuelli, R., Schiaffella, F., Bistoni, F., Pitzurra, L. & Vecchiarelli, A. (1998). Bioorg. Med. Chem. 6, 103–108.  Web of Science CrossRef CAS PubMed
First citationFujimura, K., Ota, A. & Kawashima, Y. (1996). Chem. Pharm. Bull. 44, 542–546.  CrossRef CAS PubMed
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First citationSebbar, N. K., Zerzouf, A., Essassi, E. M., Saadi, M. & El Ammari, L. (2014a). Acta Cryst. E70, o160–o161.  CSD CrossRef CAS IUCr Journals
First citationSebbar, N. K., Zerzouf, A., Essassi, E. M., Saadi, M. & El Ammari, L. (2014b). Acta Cryst. E70, o116.  CSD CrossRef IUCr Journals
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals
First citationSpek, A. L. (2009). Acta Cryst. D65, 148–155.  Web of Science CrossRef CAS IUCr Journals
First citationWestrip, S. P. (2010). J. Appl. Cryst. 43, 920–925.  Web of Science CrossRef CAS IUCr Journals
First citationZerzouf, A., Salem, M., Essassi, E. M. & Pierrot, M. (2001). Acta Cryst. E57, o498–o499.  Web of Science CSD CrossRef CAS IUCr Journals

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