organic compounds
2-[(2Z)-2-Benzylidene-3-oxo-3,4-dihydro-2H-1,4-benzothiazin-4-yl]acetic acid
aLaboratoire de Chimie Organique Hétérocyclique, Pôle de Compétences Pharmacochimie, Mohammed V University in Rabat, BP 1014, Avenue Ibn Batouta, Rabat, Morocco, bDepartment of Chemistry, Tulane University, New Orleans, LA 70118, USA, cLaboratoire de Chimie Organique Appliquée, Université Sidi Mohamed Ben Abdallah, Faculté des Sciences et Techniques, Route d'Imouzzer, BP 2202, Fez, Morocco, and dDépartement de chimie, Faculté des Sciences, Université Ibn Zohr, BP 8106, Cité Dakhla, 80000 Agadir, Morocco
*Correspondence e-mail: ellouz.chimie@gmail.com
In the title compound, C17H13NO3S, the thiazine ring displays a screw-boat conformation. The dihedral angle between the terminal benzene ring and the mean plane of the 1,4-benzothiazine fused-ring system is 51.52 (6)°. In the crystal, inversion dimers linked by pairs of O—H⋯Ot (t = thiazine) hydrogen bonds generate R22(14) loops. The dimers are linked by pairwise C—H⋯O hydrogen bonds, resulting in [010] chains.
Keywords: crystal structure; hydrogen bonding; benzothiazine.
CCDC reference: 1482425
Structure description
As a continuation of our studies of substituted 1,4-benzothiazine derivatives (Ellouz et al., 2015; Sebbar et al., 2015), we report the synthesis of a 1,4-benzothiazine derivative (Fig. 1) by the hydrolysis reaction with aqueous solution of potassium hydroxide of ethyl 2-(3-oxo-2,3-dihydro[1,4]-benzothiazin-4-yl)acetate in ethanol.
A puckering analysis of the heterocyclic ring gave parameters Q = 0.430 (1) Å, θ = 106.1 (2)° and φ = 167.5 (2)°. The dihedral angle between the C1–C6 and C10–C15 rings is 56.70 (5)°. In the crystal, pair-wise O2—H2A⋯O1i [symmetry code: (i) 2 − x, 1 − y, 2 − z) hydrogen bonds form inversion dimers, which are connected into chains running parallel to the b axis by pair-wise C16—H16A⋯O3ii [symmetry code: (ii) 2 − x, −y, 2 − z) hydrogen bonds (Table 1 and Fig. 2).
Synthesis and crystallization
A solution of potassium hydroxide (12.5 mmol) in water (5 ml) was added to the solution of ethyl (Z)-2-(2-benzylidene-2,3-dihydro-[1,4]-benzothiazin-3-one-4-yl)acetate(3.07 mmol) in ethanol (10 ml). The resulting reaction mixture was stirred at room temperature for 6 h and the reaction completion was checked by TLC. The reaction mixture was poured into water and acidified with 3 M HCl to form the title compound as a colorless solid. The solid product was purified by recrystallization from ethanol solution to afford colorless crystals in 80% yield.
Refinement
Crystal data, data collection and structure .
details are summarized in Table 2Structural data
CCDC reference: 1482425
10.1107/S2414314616008634/hb4054sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S2414314616008634/hb4054Isup2.hkl
Supporting information file. DOI: 10.1107/S2414314616008634/hb4054Isup3.cml
Data collection: APEX2 (Bruker, 2015); cell
SAINT (Bruker, 2015); data reduction: SAINT (Bruker, 2015); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: publCIF (Westrip, 2010).C17H13NO3S | Z = 2 |
Mr = 311.34 | F(000) = 324 |
Triclinic, P1 | Dx = 1.474 Mg m−3 |
a = 8.6760 (3) Å | Cu Kα radiation, λ = 1.54178 Å |
b = 8.7882 (3) Å | Cell parameters from 9893 reflections |
c = 9.8142 (4) Å | θ = 4.8–74.7° |
α = 78.200 (1)° | µ = 2.16 mm−1 |
β = 73.311 (1)° | T = 150 K |
γ = 86.242 (1)° | Block, colourless |
V = 701.61 (4) Å3 | 0.17 × 0.11 × 0.09 mm |
Bruker D8 VENTURE PHOTON 100 CMOS diffractometer | 2816 independent reflections |
Radiation source: INCOATEC IµS micro–focus source | 2698 reflections with I > 2σ(I) |
Mirror monochromator | Rint = 0.028 |
Detector resolution: 10.4167 pixels mm-1 | θmax = 74.6°, θmin = 4.8° |
ω scans | h = −10→10 |
Absorption correction: multi-scan (SADABS; Bruker, 2015) | k = −9→10 |
Tmin = 0.68, Tmax = 0.83 | l = −12→12 |
20850 measured reflections |
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)] = 0.032 | Hydrogen site location: mixed |
wR(F2) = 0.083 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0431P)2 + 0.2923P] where P = (Fo2 + 2Fc2)/3 |
2816 reflections | (Δ/σ)max = 0.001 |
203 parameters | Δρmax = 0.20 e Å−3 |
0 restraints | Δρmin = −0.32 e Å−3 |
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. |
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 > 2sigma(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. H-atoms attached to carbon were placed in calculated positions (C—H = 0.95 - 0.99 Å). All were included as riding contributions with isotropic displacement parameters 1.2 times those of the attached atoms. |
x | y | z | Uiso*/Ueq | ||
S1 | 0.61329 (4) | 0.52854 (4) | 0.64991 (3) | 0.02465 (11) | |
O1 | 0.73459 (11) | 0.46100 (11) | 1.01298 (10) | 0.0243 (2) | |
O2 | 1.08484 (12) | 0.38446 (11) | 0.88403 (10) | 0.0264 (2) | |
H2A | 1.159 (3) | 0.417 (3) | 0.922 (2) | 0.056 (6)* | |
O3 | 1.06908 (13) | 0.17480 (12) | 1.06181 (11) | 0.0322 (2) | |
N1 | 0.80930 (13) | 0.32446 (12) | 0.83337 (11) | 0.0207 (2) | |
C1 | 0.85510 (15) | 0.31621 (15) | 0.68359 (14) | 0.0206 (3) | |
C2 | 0.98019 (16) | 0.21791 (16) | 0.62797 (15) | 0.0253 (3) | |
H2 | 1.0367 | 0.1572 | 0.6903 | 0.030* | |
C3 | 1.02251 (17) | 0.20820 (17) | 0.48272 (16) | 0.0291 (3) | |
H3 | 1.1070 | 0.1400 | 0.4465 | 0.035* | |
C4 | 0.94287 (18) | 0.29701 (17) | 0.38981 (15) | 0.0294 (3) | |
H4 | 0.9717 | 0.2894 | 0.2904 | 0.035* | |
C5 | 0.82079 (17) | 0.39689 (16) | 0.44328 (15) | 0.0264 (3) | |
H5 | 0.7671 | 0.4596 | 0.3797 | 0.032* | |
C6 | 0.77588 (15) | 0.40624 (15) | 0.58941 (14) | 0.0217 (3) | |
C7 | 0.66020 (15) | 0.57311 (15) | 0.79937 (14) | 0.0207 (3) | |
C8 | 0.73771 (15) | 0.45155 (15) | 0.88811 (13) | 0.0202 (3) | |
C9 | 0.61808 (15) | 0.70741 (15) | 0.84638 (15) | 0.0230 (3) | |
H9 | 0.6471 | 0.7150 | 0.9310 | 0.028* | |
C10 | 0.53440 (15) | 0.84350 (15) | 0.78719 (14) | 0.0228 (3) | |
C11 | 0.42571 (16) | 0.83932 (16) | 0.70696 (15) | 0.0263 (3) | |
H11 | 0.4039 | 0.7434 | 0.6861 | 0.032* | |
C12 | 0.34936 (18) | 0.97462 (18) | 0.65750 (16) | 0.0318 (3) | |
H12 | 0.2765 | 0.9708 | 0.6022 | 0.038* | |
C13 | 0.37898 (18) | 1.11481 (17) | 0.68845 (17) | 0.0346 (3) | |
H13 | 0.3277 | 1.2072 | 0.6532 | 0.042* | |
C14 | 0.48335 (19) | 1.12025 (18) | 0.7708 (2) | 0.0376 (4) | |
H14 | 0.5021 | 1.2161 | 0.7937 | 0.045* | |
C15 | 0.56053 (17) | 0.98580 (17) | 0.81981 (18) | 0.0319 (3) | |
H15 | 0.6320 | 0.9903 | 0.8762 | 0.038* | |
C16 | 0.86963 (16) | 0.20705 (15) | 0.93505 (14) | 0.0229 (3) | |
H16A | 0.8936 | 0.1106 | 0.8952 | 0.027* | |
H16B | 0.7832 | 0.1831 | 1.0274 | 0.027* | |
C17 | 1.01887 (16) | 0.25291 (15) | 0.96737 (14) | 0.0222 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.02793 (18) | 0.02328 (18) | 0.02754 (18) | 0.00799 (12) | −0.01553 (13) | −0.00721 (12) |
O1 | 0.0268 (5) | 0.0251 (5) | 0.0222 (4) | 0.0002 (4) | −0.0094 (4) | −0.0041 (3) |
O2 | 0.0276 (5) | 0.0275 (5) | 0.0256 (5) | −0.0022 (4) | −0.0124 (4) | −0.0007 (4) |
O3 | 0.0417 (6) | 0.0271 (5) | 0.0335 (5) | 0.0042 (4) | −0.0232 (5) | −0.0019 (4) |
N1 | 0.0226 (5) | 0.0191 (5) | 0.0218 (5) | 0.0035 (4) | −0.0101 (4) | −0.0029 (4) |
C1 | 0.0213 (6) | 0.0196 (6) | 0.0225 (6) | −0.0009 (5) | −0.0082 (5) | −0.0041 (5) |
C2 | 0.0232 (6) | 0.0237 (6) | 0.0306 (7) | 0.0037 (5) | −0.0104 (5) | −0.0059 (5) |
C3 | 0.0259 (7) | 0.0283 (7) | 0.0334 (7) | 0.0029 (5) | −0.0055 (6) | −0.0116 (6) |
C4 | 0.0328 (7) | 0.0307 (7) | 0.0251 (7) | −0.0020 (6) | −0.0062 (6) | −0.0089 (5) |
C5 | 0.0308 (7) | 0.0261 (7) | 0.0244 (6) | −0.0006 (5) | −0.0116 (5) | −0.0036 (5) |
C6 | 0.0230 (6) | 0.0190 (6) | 0.0246 (6) | 0.0001 (5) | −0.0091 (5) | −0.0040 (5) |
C7 | 0.0183 (6) | 0.0205 (6) | 0.0236 (6) | 0.0009 (5) | −0.0073 (5) | −0.0031 (5) |
C8 | 0.0187 (6) | 0.0200 (6) | 0.0225 (6) | −0.0007 (5) | −0.0072 (5) | −0.0032 (5) |
C9 | 0.0201 (6) | 0.0230 (7) | 0.0272 (6) | 0.0016 (5) | −0.0088 (5) | −0.0053 (5) |
C10 | 0.0197 (6) | 0.0207 (6) | 0.0265 (6) | 0.0026 (5) | −0.0046 (5) | −0.0046 (5) |
C11 | 0.0264 (6) | 0.0246 (7) | 0.0289 (7) | 0.0061 (5) | −0.0095 (5) | −0.0069 (5) |
C12 | 0.0297 (7) | 0.0339 (8) | 0.0305 (7) | 0.0104 (6) | −0.0105 (6) | −0.0038 (6) |
C13 | 0.0296 (7) | 0.0242 (7) | 0.0411 (8) | 0.0068 (6) | −0.0042 (6) | 0.0035 (6) |
C14 | 0.0306 (7) | 0.0202 (7) | 0.0595 (10) | 0.0005 (6) | −0.0096 (7) | −0.0071 (6) |
C15 | 0.0254 (7) | 0.0257 (7) | 0.0473 (9) | 0.0013 (5) | −0.0125 (6) | −0.0100 (6) |
C16 | 0.0259 (6) | 0.0195 (6) | 0.0236 (6) | 0.0027 (5) | −0.0107 (5) | −0.0007 (5) |
C17 | 0.0255 (6) | 0.0219 (6) | 0.0207 (6) | 0.0061 (5) | −0.0086 (5) | −0.0061 (5) |
S1—C7 | 1.7519 (13) | C7—C9 | 1.3449 (18) |
S1—C6 | 1.7546 (13) | C7—C8 | 1.4878 (17) |
O1—C8 | 1.2376 (16) | C9—C10 | 1.4626 (18) |
O2—C17 | 1.3282 (17) | C9—H9 | 0.9500 |
O2—H2A | 0.92 (2) | C10—C11 | 1.3976 (19) |
O3—C17 | 1.2052 (16) | C10—C15 | 1.400 (2) |
N1—C8 | 1.3729 (16) | C11—C12 | 1.3905 (19) |
N1—C1 | 1.4242 (16) | C11—H11 | 0.9500 |
N1—C16 | 1.4637 (15) | C12—C13 | 1.384 (2) |
C1—C6 | 1.3954 (18) | C12—H12 | 0.9500 |
C1—C2 | 1.3970 (18) | C13—C14 | 1.384 (2) |
C2—C3 | 1.385 (2) | C13—H13 | 0.9500 |
C2—H2 | 0.9500 | C14—C15 | 1.387 (2) |
C3—C4 | 1.385 (2) | C14—H14 | 0.9500 |
C3—H3 | 0.9500 | C15—H15 | 0.9500 |
C4—C5 | 1.384 (2) | C16—C17 | 1.5154 (18) |
C4—H4 | 0.9500 | C16—H16A | 0.9900 |
C5—C6 | 1.3923 (19) | C16—H16B | 0.9900 |
C5—H5 | 0.9500 | ||
C7—S1—C6 | 100.41 (6) | C7—C9—H9 | 115.1 |
C17—O2—H2A | 109.4 (14) | C10—C9—H9 | 115.1 |
C8—N1—C1 | 124.44 (10) | C11—C10—C15 | 118.42 (12) |
C8—N1—C16 | 114.83 (10) | C11—C10—C9 | 124.55 (12) |
C1—N1—C16 | 119.46 (10) | C15—C10—C9 | 116.96 (12) |
C6—C1—C2 | 118.67 (12) | C12—C11—C10 | 120.45 (13) |
C6—C1—N1 | 120.63 (11) | C12—C11—H11 | 119.8 |
C2—C1—N1 | 120.71 (11) | C10—C11—H11 | 119.8 |
C3—C2—C1 | 120.52 (12) | C13—C12—C11 | 120.32 (14) |
C3—C2—H2 | 119.7 | C13—C12—H12 | 119.8 |
C1—C2—H2 | 119.7 | C11—C12—H12 | 119.8 |
C4—C3—C2 | 120.62 (13) | C12—C13—C14 | 119.93 (13) |
C4—C3—H3 | 119.7 | C12—C13—H13 | 120.0 |
C2—C3—H3 | 119.7 | C14—C13—H13 | 120.0 |
C5—C4—C3 | 119.30 (13) | C13—C14—C15 | 120.01 (14) |
C5—C4—H4 | 120.4 | C13—C14—H14 | 120.0 |
C3—C4—H4 | 120.4 | C15—C14—H14 | 120.0 |
C4—C5—C6 | 120.59 (13) | C14—C15—C10 | 120.83 (14) |
C4—C5—H5 | 119.7 | C14—C15—H15 | 119.6 |
C6—C5—H5 | 119.7 | C10—C15—H15 | 119.6 |
C5—C6—C1 | 120.28 (12) | N1—C16—C17 | 115.04 (11) |
C5—C6—S1 | 117.61 (10) | N1—C16—H16A | 108.5 |
C1—C6—S1 | 122.06 (10) | C17—C16—H16A | 108.5 |
C9—C7—C8 | 117.37 (12) | N1—C16—H16B | 108.5 |
C9—C7—S1 | 123.59 (10) | C17—C16—H16B | 108.5 |
C8—C7—S1 | 118.80 (9) | H16A—C16—H16B | 107.5 |
O1—C8—N1 | 119.20 (11) | O3—C17—O2 | 124.70 (13) |
O1—C8—C7 | 120.81 (11) | O3—C17—C16 | 121.37 (12) |
N1—C8—C7 | 119.97 (11) | O2—C17—C16 | 113.93 (11) |
C7—C9—C10 | 129.89 (13) | ||
C8—N1—C1—C6 | −26.36 (19) | C16—N1—C8—C7 | −175.22 (11) |
C16—N1—C1—C6 | 167.24 (12) | C9—C7—C8—O1 | 13.88 (18) |
C8—N1—C1—C2 | 153.63 (12) | S1—C7—C8—O1 | −160.73 (10) |
C16—N1—C1—C2 | −12.77 (18) | C9—C7—C8—N1 | −168.25 (12) |
C6—C1—C2—C3 | −1.1 (2) | S1—C7—C8—N1 | 17.15 (16) |
N1—C1—C2—C3 | 178.87 (12) | C8—C7—C9—C10 | −176.82 (12) |
C1—C2—C3—C4 | 0.7 (2) | S1—C7—C9—C10 | −2.5 (2) |
C2—C3—C4—C5 | 0.5 (2) | C7—C9—C10—C11 | 27.5 (2) |
C3—C4—C5—C6 | −1.2 (2) | C7—C9—C10—C15 | −155.58 (14) |
C4—C5—C6—C1 | 0.8 (2) | C15—C10—C11—C12 | 1.8 (2) |
C4—C5—C6—S1 | −176.86 (11) | C9—C10—C11—C12 | 178.69 (13) |
C2—C1—C6—C5 | 0.36 (19) | C10—C11—C12—C13 | −0.6 (2) |
N1—C1—C6—C5 | −179.65 (12) | C11—C12—C13—C14 | −0.9 (2) |
C2—C1—C6—S1 | 177.95 (10) | C12—C13—C14—C15 | 1.2 (2) |
N1—C1—C6—S1 | −2.06 (17) | C13—C14—C15—C10 | 0.0 (2) |
C7—S1—C6—C5 | −153.85 (11) | C11—C10—C15—C14 | −1.5 (2) |
C7—S1—C6—C1 | 28.50 (12) | C9—C10—C15—C14 | −178.61 (14) |
C6—S1—C7—C9 | 150.49 (12) | C8—N1—C16—C17 | −72.15 (14) |
C6—S1—C7—C8 | −35.26 (11) | C1—N1—C16—C17 | 95.52 (14) |
C1—N1—C8—O1 | −164.28 (11) | N1—C16—C17—O3 | 171.05 (12) |
C16—N1—C8—O1 | 2.69 (17) | N1—C16—C17—O2 | −8.42 (16) |
C1—N1—C8—C7 | 17.81 (18) |
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2A···O1i | 0.92 (2) | 1.78 (2) | 2.6591 (13) | 161 (2) |
C16—H16A···O3ii | 0.99 | 2.47 | 3.3583 (16) | 149 |
Symmetry codes: (i) −x+2, −y+1, −z+2; (ii) −x+2, −y, −z+2. |
Acknowledgements
The support of NSF–MRI Grant No. 1228232 for the purchase of the diffractometer and Tulane University for support of the Tulane Crystallography Laboratory are gratefully acknowledged.
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