organic compounds
Ethyl 3-methyl-1-oxo-4H-1,4-benzothiazine-2-carboxylate monohydrate
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
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)°.
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).
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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
The title compound was isolated in 36% yield and recrystallized from ethanol solution to give colorless crystals.Structural data
CCDC reference: 1849866
https://doi.org/10.1107/S2414314618008878/sj4184sup1.cif
contains datablocks global, I. DOI: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
Data collection: APEX3 (Bruker, 2016); cell
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).C12H13NO3S·H2O | F(000) = 568 |
Mr = 269.31 | Dx = 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 |
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 | Rint = 0.028 |
Detector resolution: 10.4167 pixels mm-1 | θmax = 72.3°, θmin = 4.7° |
ω scans | h = −10→10 |
Absorption correction: multi-scan (SADABS; Bruker, 2016) | k = −21→23 |
Tmin = 0.74, Tmax = 0.90 | l = −9→9 |
9610 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)] = 0.031 | Hydrogen site location: difference Fourier map |
wR(F2) = 0.078 | All H-atom parameters refined |
S = 1.09 | w = 1/[σ2(Fo2) + (0.0359P)2 + 0.6004P] where P = (Fo2 + 2Fc2)/3 |
2466 reflections | (Δ/σ)max = 0.001 |
223 parameters | Δρmax = 0.21 e Å−3 |
0 restraints | Δρmin = −0.41 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. |
x | y | z | Uiso*/Ueq | ||
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)* |
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) |
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) |
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···O2iv | 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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