2-[(2Z)-2-Benzyl­idene-3-oxo-3,4-di­hydro-2H-1,4-benzo­thia­zin-4-yl]acetic acid

Sebbar, N.K.; Ellouz, M.; Mague, J.T.; Ouzidan, Y.; Essassi, E.M.; Zouihri, H.

doi:10.1107/S2414314616008634

organic compounds

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ISSN: 2414-3146

Volume 1| Part 6| June 2016| x160863

doi:10.1107/S2414314616008634

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2-[(2Z)-2-Benzylidene-3-oxo-3,4-dihydro-2H-1,4-benzothiazin-4-yl]acetic acid

Nada Kheira Sebbar,^a Mohamed Ellouz,^a ^* Joel T. Mague,^b Younes Ouzidan,^c El Mokhtar Essassi ^a and Hafid Zouihri ^d

^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

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 27 May 2016; accepted 29 May 2016; online 17 June 2016)

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⋯O_t (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.

Figure 1
The title molecule with 50% probability ellipsoids.

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).

Table 1
Hydrogen-bond geometry (Å, °)

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.

Figure 2
A part of the unit cell showing intermolecular hydrogen bonds (dotted lines) in the crystal structure of the title compound.

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 refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₇H₁₃NO₃S
M_r	311.34
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	150
a, b, c (Å)	8.6760 (3), 8.7882 (3), 9.8142 (4)
α, β, γ (°)	78.200 (1), 73.311 (1), 86.242 (1)
V (Å³)	701.61 (4)
Z	2
Radiation type	Cu Kα
μ (mm⁻¹)	2.16
Crystal size (mm)	0.17 × 0.11 × 0.09

Data collection
Diffractometer	Bruker D8 VENTURE PHOTON 100 CMOS
Absorption correction	Multi-scan (SADABS; Bruker, 2015 )
T_min, T_max	0.68, 0.83
No. of measured, independent and observed [I > 2σ(I)] reflections	20850, 2816, 2698
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.625

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.032, 0.083, 1.04
No. of reflections	2816
No. of parameters	203
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.20, −0.32
Computer programs: APEX2 and SAINT (Bruker, 2015), SHELXT (Sheldrick, 2015a ), SHELXL2014 (Sheldrick, 2015b ), PLATON (Spek, 2009 ) and publCIF (Westrip, 2010 ).

Structural data

CCDC reference: 1482425

Crystal structure: contains datablocks global, I. DOI: 10.1107/S2414314616008634/hb4054sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2414314616008634/hb4054Isup2.hkl

Supporting information file. DOI: 10.1107/S2414314616008634/hb4054Isup3.cml

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2015); cell refinement: 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).

2-[(2Z)-2-Benzylidene-3-oxo-3,4-dihydro-2H-1,4-benzothiazin-4-yl]acetic acid top

Crystal data top

C₁₇H₁₃NO₃S	Z = 2
M_r = 311.34	F(000) = 324
Triclinic, P1	D_x = 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

Data collection top

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	R_int = 0.028
Detector resolution: 10.4167 pixels mm^-1	θ_max = 74.6°, θ_min = 4.8°
ω scans	h = −10→10
Absorption correction: multi-scan (SADABS; Bruker, 2015)	k = −9→10
T_min = 0.68, T_max = 0.83	l = −12→12
20850 measured reflections

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)] = 0.032	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(F_o²) + (0.0431P)² + 0.2923P] where P = (F_o² + 2F_c²)/3
2816 reflections	(Δ/σ)_max = 0.001
203 parameters	Δρ_max = 0.20 e Å⁻³
0 restraints	Δρ_min = −0.32 e Å⁻³

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
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)

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Hydrogen-bond geometry (Å, º) top

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.

References

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