Ethyl 3-methyl-1-oxo-4H-1,4-benzo­thia­zine-2-carboxyl­ate monohydrate

Baryala, Y.; El Bakri, Y.; Anouar, E.H.; Zerzouf, A.; Essassi, E.M.; Mague, J.T.

doi:10.1107/S2414314618008878

organic compounds

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ISSN: 2414-3146

Volume 3| Part 6| June 2018| x180887

https://doi.org/10.1107/S2414314618008878

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Ethyl 3-methyl-1-oxo-4H-1,4-benzothiazine-2-carboxylate monohydrate

Yamna Baryala,^a,^c ^* Youness El Bakri,^a El Hassane Anouar,^b Abdelfettahb Zerzouf,^c El Mokhtar Essassi ^a and Joel T. Mague ^d

^aLaboratoire de Chimie Organique Hétérocyclique, Centre de Recherche des Sciences des Médicaments, URAC 21, Pôle de Compétence Pharmacochimie, Av Ibn Battouta, BP 1014, Faculté des Sciences, Université Mohammed V, Rabat, Morocco, ^bDepartment of Chemistry, College of Science and Humanities, Prince Sattam bin Abdulaziz University, Al-Kharj, Saudi Arabia, ^cLaboratoire de Chimie Organique et Etudes Physicochimique, ENS Takaddoum, Rabat, Morocco, and ^dDepartment of Chemistry, Tulane University, New Orleans, LA 70118, USA
^*Correspondence e-mail: y.baryala@gmail.com

Edited by J. Simpson, University of Otago, New Zealand (Received 13 June 2018; accepted 17 June 2018; online 26 June 2018)

The organic molecule in the title hydrate, C₁₂H₁₃NO₃S·H₂O, is folded across the S⋯N vector. Chains two molecules thick extending along the a-axis direction are formed by N—H⋯O and O—H⋯O hydrogen bonds. These interactions are reinforced by C—H⋯S hydrogen bonds and offset π-stacking interactions between centrosymmetrically related benzene rings. The chains are associated through C—H⋯O hydrogen bonds.

Keywords: crystal structure; hydrogen bonding; π-stacking; benzothiazine; crystal structure.

CCDC reference: 1849866

Structure description

1,4-Benzothiazine derivatives constitute an important class of natural products possessing a wide range of biological and pharmaceutical activity due to the presence of the nitrogen–sulfur axis, which is considered to be one of the structural features important for their activities (Nitin et al., 2013 ; Gupta & Gupta, 2011 ). The 1,4-benzothiazine moiety is the pharmacophore of phenothiazines, which are well established anti-psychotic drugs (Barker & Miller, 1969 ), and is also known as the basic unit for their utility as dyestuffs (Bhikan & Bhata, 2015 ), photographic developers (Dabholkar & Gavande, 2016 ), ultraviolet light absorbers and antioxidants (Dabholkar & Gavande, 2010 ).

The overall shape of the title molecule (Fig. 1) may be described as an `open butterfly' hinged about the S1⋯N1 vector. A puckering analysis of the heterocyclic ring gave the parameters Q = 0.301 (1) Å, θ = 65.7 (2)° and φ = 1.7 (3)°.

Figure 1
The title molecule with labeling scheme and 50% probability ellipsoids. The O—H⋯O hydrogen bond is shown as a dashed line.

In the crystal, N1—H1⋯O4, O4—H4A⋯O1 and O4—H4B⋯O1 hydrogen bonds (Table 1) generate generate chains two molecules thick extending along the a-axis direction and inclined at approximately 56° to [001] (Fig. 2). Reinforcing the above interactions are C2—H2⋯S1 hydrogen bonds (Table 1) and offset π-stacking interactions between benzene rings across centers of symmetry with centroid–centroid distances of 3.8263 (8) Å and interplanar spacings of 3.4260 (6) Å (Fig. 2). Finally, the chains are tied together via C4—H4⋯O2 hydrogen bonds (Table 2 and Fig. 3).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O4ⁱ	0.88 (2)	1.98 (2)	2.8504 (16)	170.7 (19)
C2—H2⋯S1ⁱⁱ	0.964 (19)	2.898 (19)	3.6729 (15)	138.2 (14)
O4—H4A⋯O1	0.82 (2)	2.05 (2)	2.8458 (15)	164 (2)
O4—H4B⋯O1ⁱⁱⁱ	0.89 (2)	1.90 (2)	2.7841 (15)	175 (2)
C4—H4⋯O2^iv	0.985 (19)	2.283 (17)	3.0694 (15)	136.1 (13)
Symmetry codes: (i) x+1, y, z; (ii) -x+1, -y+1, -z; (iii) -x+1, -y+1, -z+1; (iv) $[-x+2, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Table 2
Experimental details

Crystal data
Chemical formula	C₁₂H₁₃NO₃S·H₂O
M_r	269.31
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	8.8340 (3), 18.6849 (6), 7.6927 (3)
β (°)	91.478 (1)
V (Å³)	1269.35 (8)
Z	4
Radiation type	Cu Kα
μ (mm⁻¹)	2.35
Crystal size (mm)	0.31 × 0.15 × 0.05

Data collection
Diffractometer	Bruker D8 VENTURE PHOTON 100 CMOS
Absorption correction	Multi-scan (SADABS; Bruker, 2016 )
T_min, T_max	0.74, 0.90
No. of measured, independent and observed [I > 2σ(I)] reflections	9610, 2466, 2332
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.618

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.031, 0.078, 1.09
No. of reflections	2466
No. of parameters	223
H-atom treatment	All H-atom parameters refined
Δρ_max, Δρ_min (e Å⁻³)	0.21, −0.42
Computer programs: APEX3 and SAINT (Bruker, 2016), SHELXT (Sheldrick, 2015a ), SHELXL2016 (Sheldrick, 2015b ), DIAMOND (Brandenburg & Putz, 2012 ) and SHELXTL (Sheldrick, 2008 ).

Figure 2
A portion of one chain viewed along the b-axis direction. O—H⋯O, N—H⋯O and C—H⋯S hydrogen bonds are depicted, respectively, as red, dark-blue and black dashed lines. The offset π-stacking interactions are shown as orange dashed lines.

Figure 3
Packing viewed along the a-axis direction with intermolecular interactions depicted as in Fig. 2

with the addition of light-blue dashed lines for the C—H⋯O hydrogen bonds.

Synthesis and crystallization

A mixture of 2,2-disulfanediyldianiline (0.5 g, 2 mmol) and ethyl acetoacetate (0.5 ml, 4 mmol) was refluxed at 453 K for 3 h in xylene. After cooling and filtration, the solution was then concentrated to dryness under reduced pressure. The residue obtained was chromatographed on silica gel using dichloromethane/ether (9/1) as eluent. The title compound was isolated in 36% yield and recrystallized from ethanol solution to give colorless crystals.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Structural data

CCDC reference: 1849866

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S2414314618008878/sj4184sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314618008878/sj4184Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314618008878/sj4184Isup3.cdx

Supporting information file. DOI: https://doi.org/10.1107/S2414314618008878/sj4184Isup4.cml

checkCIF report

Computing details top

Data collection: APEX3 (Bruker, 2016); cell refinement: SAINT (Bruker, 2016); data reduction: SAINT (Bruker, 2016); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2016 (Sheldrick, 2015b); molecular graphics: DIAMOND (Brandenburg & Putz, 2012); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Ethyl 3-methyl-1-oxo-4H-1λ⁴,4-benzothiazine-2-carboxylate monohydrate top

Crystal data top

C₁₂H₁₃NO₃S·H₂O	F(000) = 568
M_r = 269.31	D_x = 1.409 Mg m⁻³
Monoclinic, P2₁/c	Cu Kα radiation, λ = 1.54178 Å
a = 8.8340 (3) Å	Cell parameters from 8322 reflections
b = 18.6849 (6) Å	θ = 5.0–72.3°
c = 7.6927 (3) Å	µ = 2.35 mm⁻¹
β = 91.478 (1)°	T = 100 K
V = 1269.35 (8) Å³	Plate, colourless
Z = 4	0.31 × 0.15 × 0.05 mm

Data collection top

Bruker D8 VENTURE PHOTON 100 CMOS diffractometer	2466 independent reflections
Radiation source: INCOATEC IµS micro-focus source	2332 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.028
Detector resolution: 10.4167 pixels mm^-1	θ_max = 72.3°, θ_min = 4.7°
ω scans	h = −10→10
Absorption correction: multi-scan (SADABS; Bruker, 2016)	k = −21→23
T_min = 0.74, T_max = 0.90	l = −9→9
9610 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)] = 0.031	Hydrogen site location: difference Fourier map
wR(F²) = 0.078	All H-atom parameters refined
S = 1.09	w = 1/[σ²(F_o²) + (0.0359P)² + 0.6004P] where P = (F_o² + 2F_c²)/3
2466 reflections	(Δ/σ)_max = 0.001
223 parameters	Δρ_max = 0.21 e Å⁻³
0 restraints	Δρ_min = −0.41 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.

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

	x	y	z	U_iso*/U_eq
S1	0.66513 (4)	0.40943 (2)	0.17180 (4)	0.01696 (11)
O1	0.57044 (11)	0.42958 (5)	0.32582 (13)	0.0221 (2)
O2	0.86274 (14)	0.22973 (6)	0.2877 (2)	0.0436 (3)
O3	0.63340 (11)	0.26569 (5)	0.19465 (14)	0.0253 (2)
N1	0.98546 (14)	0.45089 (6)	0.31178 (15)	0.0204 (3)
H1	1.074 (2)	0.4638 (11)	0.355 (3)	0.038 (5)*
C1	0.77255 (15)	0.48632 (7)	0.12616 (17)	0.0182 (3)
C2	0.70433 (17)	0.53641 (8)	0.01453 (18)	0.0224 (3)
H2	0.612 (2)	0.5229 (10)	−0.046 (2)	0.029 (5)*
C3	0.76857 (18)	0.60286 (8)	−0.0078 (2)	0.0259 (3)
H3	0.720 (2)	0.6385 (11)	−0.081 (2)	0.032 (5)*
C4	0.90414 (17)	0.61925 (8)	0.08057 (19)	0.0251 (3)
H4	0.952 (2)	0.6665 (10)	0.068 (2)	0.031 (5)*
C5	0.97550 (17)	0.56955 (8)	0.18726 (19)	0.0225 (3)
H5	1.073 (2)	0.5811 (9)	0.245 (2)	0.023 (4)*
C6	0.91021 (15)	0.50198 (7)	0.21074 (17)	0.0187 (3)
C7	0.94695 (15)	0.38111 (8)	0.32003 (17)	0.0197 (3)
C8	0.81306 (15)	0.35467 (7)	0.24803 (18)	0.0192 (3)
C9	1.06292 (17)	0.33497 (9)	0.4119 (2)	0.0266 (3)
H9A	1.015 (2)	0.3080 (11)	0.505 (3)	0.038 (5)*
H9B	1.103 (2)	0.2996 (11)	0.334 (3)	0.039 (5)*
H9C	1.142 (2)	0.3650 (12)	0.458 (3)	0.041 (5)*
C10	0.77751 (16)	0.27792 (8)	0.24753 (19)	0.0232 (3)
C11	0.58618 (19)	0.19092 (8)	0.1915 (2)	0.0301 (3)
H11A	0.596 (2)	0.1731 (11)	0.308 (3)	0.041 (5)*
H11B	0.656 (2)	0.1661 (11)	0.112 (3)	0.044 (6)*
C12	0.4257 (2)	0.18889 (10)	0.1244 (3)	0.0348 (4)
H12A	0.360 (3)	0.2185 (13)	0.195 (3)	0.051 (6)*
H12B	0.422 (3)	0.2062 (12)	0.006 (3)	0.049 (6)*
H12C	0.391 (2)	0.1366 (12)	0.124 (3)	0.046 (6)*
O4	0.28682 (12)	0.49043 (7)	0.41229 (16)	0.0331 (3)
H4A	0.359 (3)	0.4700 (12)	0.370 (3)	0.043 (6)*
H4B	0.327 (3)	0.5176 (12)	0.496 (3)	0.047 (6)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.01205 (18)	0.01823 (18)	0.02045 (18)	0.00045 (11)	−0.00286 (12)	−0.00170 (11)
O1	0.0151 (5)	0.0248 (5)	0.0265 (5)	0.0017 (4)	0.0029 (4)	−0.0026 (4)
O2	0.0310 (7)	0.0222 (6)	0.0762 (9)	0.0054 (5)	−0.0220 (6)	−0.0006 (6)
O3	0.0195 (5)	0.0185 (5)	0.0375 (6)	−0.0020 (4)	−0.0066 (4)	−0.0006 (4)
N1	0.0131 (6)	0.0242 (6)	0.0236 (6)	0.0004 (5)	−0.0038 (5)	−0.0044 (5)
C1	0.0145 (7)	0.0199 (7)	0.0203 (6)	0.0003 (5)	0.0002 (5)	−0.0025 (5)
C2	0.0170 (7)	0.0264 (7)	0.0236 (7)	−0.0011 (5)	−0.0007 (5)	0.0008 (6)
C3	0.0250 (8)	0.0247 (7)	0.0280 (7)	0.0005 (6)	0.0015 (6)	0.0042 (6)
C4	0.0251 (8)	0.0220 (7)	0.0284 (7)	−0.0042 (6)	0.0051 (6)	−0.0030 (6)
C5	0.0176 (7)	0.0249 (7)	0.0252 (7)	−0.0037 (5)	0.0021 (5)	−0.0067 (6)
C6	0.0154 (7)	0.0213 (7)	0.0195 (6)	0.0015 (5)	0.0011 (5)	−0.0044 (5)
C7	0.0157 (7)	0.0237 (7)	0.0198 (6)	0.0024 (5)	−0.0005 (5)	−0.0035 (5)
C8	0.0146 (7)	0.0198 (7)	0.0230 (7)	0.0017 (5)	−0.0017 (5)	−0.0016 (5)
C9	0.0171 (7)	0.0292 (8)	0.0332 (8)	0.0031 (6)	−0.0076 (6)	−0.0008 (6)
C10	0.0187 (7)	0.0224 (7)	0.0282 (7)	0.0016 (5)	−0.0040 (6)	−0.0029 (5)
C11	0.0319 (9)	0.0194 (7)	0.0384 (9)	−0.0055 (6)	−0.0066 (7)	−0.0007 (6)
C12	0.0293 (9)	0.0318 (9)	0.0429 (10)	−0.0094 (7)	−0.0049 (7)	−0.0019 (8)
O4	0.0149 (6)	0.0489 (7)	0.0355 (6)	0.0018 (5)	−0.0026 (5)	−0.0184 (5)

Geometric parameters (Å, º) top

S1—O1	1.5154 (10)	C5—C6	1.402 (2)
S1—C8	1.7490 (14)	C5—H5	0.986 (19)
S1—C1	1.7621 (14)	C7—C8	1.3842 (19)
O2—C10	1.2088 (19)	C7—C9	1.5015 (19)
O3—C10	1.3460 (18)	C8—C10	1.468 (2)
O3—C11	1.4581 (18)	C9—H9A	0.98 (2)
N1—C7	1.3494 (19)	C9—H9B	0.96 (2)
N1—C6	1.3895 (18)	C9—H9C	0.96 (2)
N1—H1	0.88 (2)	C11—C12	1.497 (2)
C1—C6	1.3953 (19)	C11—H11A	0.96 (2)
C1—C2	1.396 (2)	C11—H11B	0.99 (2)
C2—C3	1.378 (2)	C12—H12A	0.97 (2)
C2—H2	0.964 (19)	C12—H12B	0.97 (2)
C3—C4	1.396 (2)	C12—H12C	1.02 (2)
C3—H3	0.97 (2)	O4—H4A	0.82 (2)
C4—C5	1.381 (2)	O4—H4B	0.89 (2)
C4—H4	0.985 (19)

O1—S1—C8	107.82 (6)	C8—C7—C9	123.30 (13)
O1—S1—C1	105.32 (6)	C7—C8—C10	122.02 (13)
C8—S1—C1	98.18 (6)	C7—C8—S1	123.28 (11)
C10—O3—C11	115.82 (11)	C10—C8—S1	114.37 (10)
C7—N1—C6	124.93 (12)	C7—C9—H9A	109.8 (12)
C7—N1—H1	118.1 (14)	C7—C9—H9B	111.0 (12)
C6—N1—H1	115.6 (14)	H9A—C9—H9B	105.9 (17)
C6—C1—C2	120.22 (13)	C7—C9—H9C	108.7 (13)
C6—C1—S1	123.06 (11)	H9A—C9—H9C	110.5 (17)
C2—C1—S1	116.29 (10)	H9B—C9—H9C	110.8 (17)
C3—C2—C1	120.54 (14)	O2—C10—O3	121.94 (14)
C3—C2—H2	121.5 (11)	O2—C10—C8	126.52 (14)
C1—C2—H2	118.0 (11)	O3—C10—C8	111.54 (12)
C2—C3—C4	119.21 (14)	O3—C11—C12	107.35 (13)
C2—C3—H3	121.1 (11)	O3—C11—H11A	107.3 (12)
C4—C3—H3	119.7 (11)	C12—C11—H11A	112.3 (13)
C5—C4—C3	120.98 (14)	O3—C11—H11B	106.1 (12)
C5—C4—H4	118.0 (11)	C12—C11—H11B	111.9 (12)
C3—C4—H4	121.0 (11)	H11A—C11—H11B	111.5 (17)
C4—C5—C6	119.95 (13)	C11—C12—H12A	111.5 (14)
C4—C5—H5	120.2 (10)	C11—C12—H12B	109.2 (14)
C6—C5—H5	119.8 (10)	H12A—C12—H12B	108.9 (19)
N1—C6—C1	121.02 (12)	C11—C12—H12C	107.8 (12)
N1—C6—C5	119.89 (13)	H12A—C12—H12C	111.0 (18)
C1—C6—C5	119.04 (13)	H12B—C12—H12C	108.4 (17)
N1—C7—C8	122.67 (13)	H4A—O4—H4B	104 (2)
N1—C7—C9	114.02 (12)

O1—S1—C1—C6	85.12 (12)	C6—N1—C7—C8	−10.1 (2)
C8—S1—C1—C6	−25.97 (13)	C6—N1—C7—C9	169.10 (13)
O1—S1—C1—C2	−87.29 (11)	N1—C7—C8—C10	175.71 (13)
C8—S1—C1—C2	161.62 (11)	C9—C7—C8—C10	−3.5 (2)
C6—C1—C2—C3	−2.8 (2)	N1—C7—C8—S1	−11.2 (2)
S1—C1—C2—C3	169.89 (11)	C9—C7—C8—S1	169.57 (11)
C1—C2—C3—C4	1.0 (2)	O1—S1—C8—C7	−83.78 (13)
C2—C3—C4—C5	1.1 (2)	C1—S1—C8—C7	25.27 (13)
C3—C4—C5—C6	−1.3 (2)	O1—S1—C8—C10	89.75 (11)
C7—N1—C6—C1	9.2 (2)	C1—S1—C8—C10	−161.20 (11)
C7—N1—C6—C5	−168.34 (13)	C11—O3—C10—O2	0.9 (2)
C2—C1—C6—N1	−175.06 (12)	C11—O3—C10—C8	−179.32 (12)
S1—C1—C6—N1	12.82 (18)	C7—C8—C10—O2	−9.4 (2)
C2—C1—C6—C5	2.5 (2)	S1—C8—C10—O2	177.01 (15)
S1—C1—C6—C5	−169.63 (10)	C7—C8—C10—O3	170.85 (12)
C4—C5—C6—N1	177.08 (13)	S1—C8—C10—O3	−2.77 (16)
C4—C5—C6—C1	−0.5 (2)	C10—O3—C11—C12	−178.26 (13)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O4ⁱ	0.88 (2)	1.98 (2)	2.8504 (16)	170.7 (19)
C2—H2···S1ⁱⁱ	0.964 (19)	2.898 (19)	3.6729 (15)	138.2 (14)
O4—H4A···O1	0.82 (2)	2.05 (2)	2.8458 (15)	164 (2)
O4—H4B···O1ⁱⁱⁱ	0.89 (2)	1.90 (2)	2.7841 (15)	175 (2)
C4—H4···O2^iv	0.985 (19)	2.283 (17)	3.0694 (15)	136.1 (13)

Symmetry codes: (i) x+1, y, z; (ii) −x+1, −y+1, −z; (iii) −x+1, −y+1, −z+1; (iv) −x+2, y+1/2, −z+1/2.

Funding information

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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