organic compounds Acta Crystallographica Section E
Experimental
Structure Reports Online
Crystal data
ISSN 1600-5368
(2Z)-2-Benzylidene-4-(prop-2-yn-1-yl)2H-1,4-benzothiazin-3(4H)-one
C18H13NOS Mr = 291.35 Orthorhombic, Pbca ˚ a = 9.0254 (13) A ˚ b = 7.7388 (12) A ˚ c = 42.488 (7) A
˚3 V = 2967.6 (8) A Z=8 Mo K radiation = 0.22 mm 1 T = 296 K 0.42 0.36 0.31 mm
Data collection
Nada Kheira Sebbar,a* Abdelfettah Zerzouf,b El Mokhtar Essassi,a Mohamed Saadic and Lahcen El Ammaric a
Laboratoire de Chimie Organique He´te´rocyclique URAC 21, Poˆle de Compe´tence Pharmacochimie, Av. Ibn Battouta, BP 1014, Faculte´ des Sciences, Universite´ Mohammed V-Agdal, Rabat, Morocco, bLaboratoire de Chimie Organique et Etudes Physicochimiques, ENS Takaddoum, Rabat, Morocco, and cLaboratoire de Chimie du Solide Applique´e, Faculte´ des Sciences, Universite´ Mohammed V-Agdal, Avenue Ibn Battouta, BP 1014, Rabat, Morocco Correspondence e-mail: [emailprotected]
Bruker X8 APEX diffractometer Absorption correction: multi-scan (SADABS; Bruker, 2009) Tmin = 0.579, Tmax = 0.746
14350 measured reflections 3248 independent reflections 2227 reflections with I > 2(I) Rint = 0.038
Refinement R[F 2 > 2(F 2)] = 0.046 wR(F 2) = 0.124 S = 1.02 3248 reflections
190 parameters H-atom parameters constrained ˚ 3 max = 0.24 e A ˚ 3 min = 0.30 e A
Received 22 April 2014; accepted 23 April 2014
˚; Key indicators: single-crystal X-ray study; T = 296 K; mean (C–C) = 0.004 A R factor = 0.046; wR factor = 0.124; data-to-parameter ratio = 17.1.
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-yn1-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.
Data collection: APEX2 (Bruker, 2009); cell refinement: SAINTPlus (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).
The authors thank the Unit of Support for Technical and Scientific Research (UATRS, CNRST) for the X-ray measurements. Supporting information for this paper is available from the IUCr electronic archives (Reference: TK5310).
References 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).
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Aotsuka, T., Hosono, H., Kurihara, T., Nakamura, Y., Matsui, T. & Kobayashi, F. (1994). Chem. Pharm. Bull. 42, 1264–1271. Bruker (2009). APEX2, SAINT-Plus and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Cremer, D. & Pople, J. A. (1975). J. Am. Chem. Soc. 97, 1354–1358. Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Fringuelli, R., Schiaffella, F., Bistoni, F., Pitzurra, L. & Vecchiarelli, A. (1998). Bioorg. Med. Chem. 6, 103–108. Fujimura, K., Ota, A. & Kawashima, Y. (1996). Chem. Pharm. Bull. 44, 542– 546. Rathore, B. S. & Kumar, M. (2006). Bioorg. Med. Chem. 14, 5678–5682. Sebbar, N. K., Zerzouf, A., Essassi, E. M., Saadi, M. & El Ammari, L. (2014a). Acta Cryst. E70, o160–o161. Sebbar, N. K., Zerzouf, A., Essassi, E. M., Saadi, M. & El Ammari, L. (2014b). Acta Cryst. E70, o116. Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Spek, A. L. (2009). Acta Cryst. D65, 148–155. Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Zerzouf, A., Salem, M., Essassi, E. M. & Pierrot, M. (2001). Acta Cryst. E57, o498–o499.
doi:10.1107/S1600536814009179
Acta Cryst. (2014). E70, o614
supplementary materials
supplementary materials Acta Cryst. (2014). E70, o614
[doi:10.1107/S1600536814009179]
(2Z)-2-Benzylidene-4-(prop-2-yn-1-yl)-2H-1,4-benzothiazin-3(4H)-one Nada Kheira Sebbar, Abdelfettah Zerzouf, El Mokhtar Essassi, Mohamed Saadi and Lahcen El Ammari 1. Chemical context 2. Structural commentary 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)°. 3. Supramolecular features 4. Database survey 5. Synthesis and crystallization 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). 6. Refinement 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).
Acta Cryst. (2014). E70, o614
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Figure 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 Crystal data C18H13NOS Mr = 291.35 Orthorhombic, Pbca Hall symbol: -P 2ac 2ab a = 9.0254 (13) Å b = 7.7388 (12) Å c = 42.488 (7) Å V = 2967.6 (8) Å3 Z=8 F(000) = 1216
Dx = 1.304 Mg m−3 Melting point: 404 K Mo Kα radiation, λ = 0.71073 Å Cell parameters from 3248 reflections θ = 2.5–27.1° µ = 0.22 mm−1 T = 296 K Block, yellow 0.42 × 0.36 × 0.31 mm
Data collection Bruker X8 APEX diffractometer Radiation source: fine-focus sealed tube Graphite monochromator φ and ω scans Absorption correction: multi-scan (SADABS; Bruker, 2009) Tmin = 0.579, Tmax = 0.746
Acta Cryst. (2014). E70, o614
14350 measured reflections 3248 independent reflections 2227 reflections with I > 2σ(I) Rint = 0.038 θmax = 27.1°, θmin = 2.5° h = −10→11 k = −5→9 l = −54→42
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supplementary materials Refinement Refinement on F2 Least-squares matrix: full R[F2 > 2σ(F2)] = 0.046 wR(F2) = 0.124 S = 1.02 3248 reflections 190 parameters 0 restraints Primary atom site location: structure-invariant direct methods
Secondary atom site location: difference Fourier map Hydrogen site location: inferred from neighbouring sites H-atom parameters constrained w = 1/[σ2(Fo2) + (0.0511P)2 + 0.8991P] where P = (Fo2 + 2Fc2)/3 (Δ/σ)max < 0.001 Δρmax = 0.24 e Å−3 Δρmin = −0.30 e Å−3
Special details 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)
C1 C2 H2 C3 H3 C4 H4 C5 H5 C6 C7 C8 C9 H9 C10 C11 H11 C12 H12 C13 H13 C14 H14 C15 H15 C16
x
y
z
Uiso*/Ueq
0.2609 (2) 0.1083 (2) 0.0443 0.0518 (2) −0.0501 0.1463 (2) 0.1081 0.2986 (2) 0.3618 0.35728 (19) 0.5877 (2) 0.5034 (2) 0.5746 (2) 0.6729 0.5260 (2) 0.6072 (3) 0.6905 0.5674 (4) 0.6237 0.4463 (3) 0.4196 0.3653 (3) 0.2826 0.4043 (3) 0.3478 0.6078 (2)
0.8787 (2) 0.8810 (3) 0.8448 0.9359 (3) 0.9412 0.9829 (3) 1.0198 0.9758 (3) 1.0037 0.9276 (2) 0.8372 (3) 0.7547 (3) 0.6372 (3) 0.6203 0.5307 (3) 0.3823 (4) 0.3577 0.2717 (5) 0.1730 0.3036 (4) 0.2274 0.4485 (4) 0.4716 0.5618 (3) 0.6608 1.0153 (3)
0.10840 (5) 0.10322 (6) 0.1191 0.07502 (6) 0.0720 0.05121 (6) 0.0320 0.05563 (5) 0.0391 0.08436 (5) 0.11202 (5) 0.13808 (5) 0.15553 (5) 0.1498 0.18189 (5) 0.18816 (7) 0.1761 0.21174 (8) 0.2154 0.23001 (7) 0.2460 0.22456 (6) 0.2369 0.20089 (5) 0.1977 0.06611 (5)
0.0479 (5) 0.0565 (6) 0.068* 0.0615 (6) 0.074* 0.0606 (6) 0.073* 0.0531 (5) 0.064* 0.0438 (5) 0.0476 (5) 0.0479 (5) 0.0552 (5) 0.066* 0.0570 (5) 0.0896 (9) 0.107* 0.1084 (11) 0.130* 0.0863 (8) 0.104* 0.0762 (7) 0.091* 0.0671 (6) 0.081* 0.0508 (5)
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supplementary materials H16A H16B C17 C18 H18 N1 O1 S1
0.5557 0.6966 0.6504 (2) 0.6844 (3) 0.7116 0.51305 (15) 0.72273 (14) 0.32280 (6)
1.1143 1.0574 0.9004 (3) 0.8080 (4) 0.7341 0.9304 (2) 0.8256 (2) 0.82420 (9)
0.0575 0.0764 0.04036 (5) 0.01999 (6) 0.0037 0.08949 (4) 0.11070 (4) 0.145920 (14)
0.061* 0.061* 0.0532 (5) 0.0761 (7) 0.091* 0.0455 (4) 0.0649 (4) 0.0667 (2)
Atomic displacement parameters (Å2)
C1 C2 C3 C4 C5 C6 C7 C8 C9 C10 C11 C12 C13 C14 C15 C16 C17 C18 N1 O1 S1
U11
U22
U33
U12
U13
U23
0.0428 (9) 0.0426 (10) 0.0394 (10) 0.0519 (11) 0.0457 (10) 0.0371 (9) 0.0424 (10) 0.0468 (10) 0.0527 (11) 0.0606 (12) 0.0892 (18) 0.117 (3) 0.099 (2) 0.0838 (16) 0.0807 (15) 0.0395 (9) 0.0492 (11) 0.0952 (18) 0.0373 (7) 0.0399 (7) 0.0603 (3)
0.0399 (10) 0.0505 (12) 0.0539 (12) 0.0600 (13) 0.0527 (12) 0.0355 (9) 0.0479 (11) 0.0494 (11) 0.0587 (13) 0.0624 (14) 0.100 (2) 0.110 (2) 0.094 (2) 0.094 (2) 0.0700 (15) 0.0467 (11) 0.0534 (12) 0.0717 (17) 0.0437 (9) 0.0831 (11) 0.0835 (4)
0.0610 (13) 0.0763 (16) 0.0912 (18) 0.0698 (15) 0.0610 (14) 0.0586 (13) 0.0525 (12) 0.0476 (11) 0.0543 (13) 0.0481 (12) 0.0790 (19) 0.098 (2) 0.0654 (18) 0.0507 (14) 0.0506 (14) 0.0662 (14) 0.0569 (14) 0.0614 (16) 0.0555 (10) 0.0718 (10) 0.0565 (4)
0.0036 (8) 0.0000 (9) 0.0034 (9) 0.0084 (10) −0.0002 (9) 0.0003 (7) −0.0026 (8) −0.0006 (9) −0.0017 (10) −0.0023 (10) 0.0273 (16) 0.032 (2) −0.0107 (17) −0.0108 (15) 0.0014 (13) −0.0037 (8) 0.0037 (9) 0.0160 (14) −0.0022 (6) −0.0003 (7) 0.0174 (3)
0.0089 (9) 0.0150 (11) −0.0007 (11) −0.0087 (11) 0.0028 (10) 0.0039 (8) 0.0020 (8) 0.0022 (9) −0.0018 (10) −0.0088 (10) 0.0084 (15) 0.006 (2) −0.0083 (16) 0.0001 (13) 0.0015 (12) 0.0062 (9) 0.0078 (10) 0.0134 (14) 0.0045 (7) 0.0004 (7) 0.0176 (3)
−0.0108 (9) −0.0098 (11) −0.0134 (13) −0.0048 (12) −0.0015 (10) −0.0079 (9) −0.0078 (10) −0.0093 (10) −0.0070 (11) −0.0051 (11) 0.0242 (17) 0.045 (2) 0.0213 (16) −0.0006 (14) −0.0025 (12) 0.0011 (10) 0.0095 (11) 0.0044 (14) −0.0020 (8) 0.0077 (9) 0.0016 (3)
Geometric parameters (Å, º) C1—C6 C1—C2 C1—S1 C2—C3 C2—H2 C3—C4 C3—H3 C4—C5 C4—H4 C5—C6 C5—H5 C6—N1 C7—O1 C7—N1
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1.394 (3) 1.394 (3) 1.741 (2) 1.369 (3) 0.9300 1.372 (3) 0.9300 1.389 (3) 0.9300 1.382 (3) 0.9300 1.423 (2) 1.224 (2) 1.375 (2)
C9—H9 C10—C15 C10—C11 C11—C12 C11—H11 C12—C13 C12—H12 C13—C14 C13—H13 C14—C15 C14—H14 C15—H15 C16—C17 C16—N1
0.9300 1.384 (3) 1.388 (3) 1.366 (4) 0.9300 1.363 (4) 0.9300 1.358 (4) 0.9300 1.380 (3) 0.9300 0.9300 1.461 (3) 1.466 (2)
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supplementary materials C7—C8 C8—C9 C8—S1 C9—C10
1.488 (3) 1.338 (3) 1.7482 (19) 1.458 (3)
C16—H16A C16—H16B C17—C18 C18—H18
0.9700 0.9700 1.164 (3) 0.9300
C6—C1—C2 C6—C1—S1 C2—C1—S1 C3—C2—C1 C3—C2—H2 C1—C2—H2 C2—C3—C4 C2—C3—H3 C4—C3—H3 C3—C4—C5 C3—C4—H4 C5—C4—H4 C6—C5—C4 C6—C5—H5 C4—C5—H5 C5—C6—C1 C5—C6—N1 C1—C6—N1 O1—C7—N1 O1—C7—C8 N1—C7—C8 C9—C8—C7 C9—C8—S1 C7—C8—S1 C8—C9—C10 C8—C9—H9 C10—C9—H9 C15—C10—C11 C15—C10—C9
119.8 (2) 122.42 (15) 117.68 (16) 120.6 (2) 119.7 119.7 119.73 (19) 120.1 120.1 120.3 (2) 119.8 119.8 120.6 (2) 119.7 119.7 118.78 (17) 120.64 (17) 120.57 (18) 119.64 (18) 120.80 (19) 119.54 (16) 117.30 (18) 123.48 (16) 119.10 (15) 131.7 (2) 114.1 114.1 116.8 (2) 126.0 (2)
C11—C10—C9 C12—C11—C10 C12—C11—H11 C10—C11—H11 C13—C12—C11 C13—C12—H12 C11—C12—H12 C14—C13—C12 C14—C13—H13 C12—C13—H13 C13—C14—C15 C13—C14—H14 C15—C14—H14 C14—C15—C10 C14—C15—H15 C10—C15—H15 C17—C16—N1 C17—C16—H16A N1—C16—H16A C17—C16—H16B N1—C16—H16B H16A—C16—H16B C18—C17—C16 C17—C18—H18 C7—N1—C6 C7—N1—C16 C6—N1—C16 C1—S1—C8
117.1 (2) 121.3 (3) 119.3 119.3 121.0 (3) 119.5 119.5 118.9 (3) 120.5 120.5 120.8 (3) 119.6 119.6 121.1 (2) 119.4 119.4 112.83 (16) 109.0 109.0 109.0 109.0 107.8 179.5 (2) 180.0 125.65 (16) 114.90 (15) 118.65 (16) 101.50 (9)
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