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Acta Crystallogr Sect E Struct Rep Online. 2008 May 1; 64(Pt 5): o788.
Published online 2008 April 2. doi:  10.1107/S1600536808007721
PMCID: PMC2961329

1-(4-Hydr­oxy-2-methyl-1,1-dioxo-2H-1,2-benzothia­zin-3-yl)ethanone

Abstract

In the title compound, C11H11NO4S, the thia­zine ring adopts a distorted half-chair conformation. The enolic H atom is involved in an intra­molecular O—H(...)O hydrogen bond, forming a six-membered ring. Mol­ecules are linked through weak inter­molecular C—H(...)O hydrogen bonds, resulting in chains lying along the b axis.

Related literature

For related literature, see: Bihovsky et al. (2004 [triangle]); Fabiola et al. (1998 [triangle]); Golič & Leban (1987 [triangle]); Zia-ur-Rehman et al. (2005 [triangle], 2006 [triangle], 2007 [triangle]); Turck et al. (1996 [triangle]).

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Object name is e-64-0o788-scheme1.jpg

Experimental

Crystal data

  • C11H11NO4S
  • M r = 253.27
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-0o788-efi1.jpg
  • a = 6.8523 (1) Å
  • b = 8.3222 (2) Å
  • c = 10.4880 (2) Å
  • α = 72.1321 (11)°
  • β = 77.9619 (12)°
  • γ = 80.0360 (12)°
  • V = 552.89 (2) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 0.29 mm−1
  • T = 120 (2) K
  • 0.40 × 0.20 × 0.14 mm

Data collection

  • Bruker–Nonius KappaCCD diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 2007 [triangle]) T min = 0.891, T max = 0.960
  • 12691 measured reflections
  • 2529 independent reflections
  • 2248 reflections with I > 2σ(I)
  • R int = 0.033

Refinement

  • R[F 2 > 2σ(F 2)] = 0.034
  • wR(F 2) = 0.092
  • S = 1.11
  • 2529 reflections
  • 157 parameters
  • H-atom parameters constrained
  • Δρmax = 0.31 e Å−3
  • Δρmin = −0.53 e Å−3

Data collection: COLLECT (Nonius, 1998 [triangle]); cell refinement: DENZO (Otwinowski & Minor, 1997 [triangle]); data reduction: DENZO and COLLECT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: CAMERON (Pearce & Watkin, 1993 [triangle]); software used to prepare material for publication: WinGX (Farrugia, 1999 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808007721/pv2072sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808007721/pv2072Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

We gratefully acknowledge the Higher Education Commission of Pakistan and the University of the Punjab, Lahore, for financial support.

supplementary crystallographic information

Comment

In order to discover new useful therapeutic agents, many new compounds are continuously being synthesized. Benzothiazine dioxides and their derivatives are reported to possess numerous types of biological activities. Owing to their applications as non-steroidal anti-inflammatory compounds (Turck et al., 1996), considerable attention has been given to 1,2-benzothiazine 1,1-dioxides and their precursor intermediates (Golič & Leban, 1987). Various 1,2-benzothiazines derivatives are also known as potent calpain I inhibitors (Bihovsky et al., 2004), while benzothiaine-3-yl-quinazolin-4-ones showed marked activity against Bacillus subtilis (Zia-ur-Rehman et al., 2006). As part of a research program synthesizing various bioactive benzothiazines (Zia-ur-Rehman et al., 2005, 2006), we herein report the crystal structure of the title compound, (I).

In the molecule of the title compound (Fig. 1), the thiazine ring exhibits a distorted half-chair conformation with S1/C1/C6/C7 atoms lying in a plane and N1 showing significant departure from the plane due to its pyramidal geometry projecting the methyl group approximately perpendicular to the ring; the deviations of N1 and C8 from the least square plane being -0.895 (2) and -0.413 (3) Å, respectively. Like other 1,2-benzothiazine 1,1-dioxide derivatives (Fabiola et al., 1998; Zia-ur-Rehman et al., 2007), the enolic hydrogen on O3 is involved in intramolecular hydrogen bonding (Table 1). Also, C7—C8 bond length [1.378 Å] (very close to normal C?C bond; 1.36 Å) indicates a partial double-bond character indicating the dominance of enolic form in the molecule. The C1—S1 bond distance [1.7580 (14) Å] is as expected for typical C(sp2)—S bond (1.751 Å).

Each molecule is linked to its adjacent one through a hydrogen bond [C4—H4···O2] resulting in a chain of molecules lying along the b axis (Table 1 and Fig. 2). Each molecule in the chain is linked with its neighbour through weak slipped π-π interactions at inversion centres; the closest C–C contacts are between C3–C3i separated by 3.316 Å.

Experimental

A mixture of 1-(4-hydroxy-1,1-dioxido-2H-1,2-benzothiazin-3-yl) ethanone (239 mg, 1.0 mmol) dissolved in acetone (10 ml), aqueous NaOH (3 ml, 5%) and dimethyl sulfate (0.5 ml) was stirred for half an hour followed by careful addition of dilute HCl (5%) to maintain the pH to Congo Red. Precipitates of (I) thus obtained were filtered, washed with water and dried. Colourless crystals were grown by slow evaporation of a solution of (I) in methanol at room temperature.

Refinement

The hydrogen atoms were included in the refinements in a riding mode with the following constraints: aryl, methyl and hydroxyl C/O—H distances 0.95, 0.98 and 0.84 Å, respectively, and Uiso(H) = 1.2 Ueq(aryl C) and 1.5 Ueq(methyl C and O).

Figures

Fig. 1.
The molecular structure of (I), showing displacement ellipsoids at the 50% probability level for non-H atoms; dashed lines denote hydrogen bonds.
Fig. 2.
Unit cell packing of (I), showing intermolecular H-bonds resulting in the chains of molecules lying along the b axis; H atoms not involved in H-bonding have been omitted.

Crystal data

C11H11NO4SZ = 2
Mr = 253.27F000 = 264
Triclinic, P1Dx = 1.521 Mg m3
Hall symbol: -P 1Mo Kα radiation λ = 0.71073 Å
a = 6.8523 (1) ÅCell parameters from 15360 reflections
b = 8.3222 (2) Åθ = 2.9–27.5º
c = 10.4880 (2) ŵ = 0.30 mm1
α = 72.1321 (11)ºT = 120 (2) K
β = 77.9619 (12)ºShard, colourless
γ = 80.0360 (12)º0.40 × 0.20 × 0.14 mm
V = 552.892 (19) Å3

Data collection

Bruker–Nonius CCD camera on κ-goniostat diffractometer2529 independent reflections
Radiation source: Bruker Nonius FR591 Rotating Anode2248 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.033
Detector resolution: 9.091 pixels mm-1θmax = 27.5º
T = 120(2) Kθmin = 3.1º
[var phi] & ω scans to fill the asymmetric unith = −8→8
Absorption correction: multi-scan(SADABS; Sheldrick, 2007)k = −10→10
Tmin = 0.891, Tmax = 0.960l = −13→13
12691 measured reflections

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.034H-atom parameters constrained
wR(F2) = 0.092  w = 1/[σ2(Fo2) + (0.041P)2 + 0.3066P] where P = (Fo2 + 2Fc2)/3
S = 1.11(Δ/σ)max = 0.030
2529 reflectionsΔρmax = 0.31 e Å3
157 parametersΔρmin = −0.53 e Å3
Primary atom site location: structure-invariant direct methodsExtinction correction: none

Special details

Experimental. SADABS was used to perform the Absorption correction Estimated minimum and maximum transmission: 0.6696 0.7456 The given Tmin and Tmax were generated using the SHELX SIZE command
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)

xyzUiso*/Ueq
C10.3007 (2)0.32223 (18)0.37041 (14)0.0135 (3)
C20.2992 (2)0.31686 (19)0.50412 (15)0.0164 (3)
H20.32460.21170.57020.020*
C30.2595 (2)0.4692 (2)0.53933 (16)0.0191 (3)
H30.25750.46840.63040.023*
C40.2228 (2)0.6220 (2)0.44168 (16)0.0199 (3)
H40.19730.72520.46650.024*
C50.2229 (2)0.62640 (19)0.30802 (15)0.0184 (3)
H50.19830.73200.24220.022*
C60.2593 (2)0.47505 (18)0.27093 (14)0.0148 (3)
C70.2558 (2)0.47385 (19)0.13150 (14)0.0153 (3)
C80.2396 (2)0.32881 (19)0.09905 (14)0.0157 (3)
C90.2507 (2)0.3316 (2)−0.04098 (16)0.0204 (3)
C100.2518 (3)0.1701 (2)−0.07671 (18)0.0332 (4)
H10A0.11360.1532−0.07640.050*
H10B0.31130.0740−0.00980.050*
H10C0.33100.1775−0.16720.050*
C110.0024 (2)0.1379 (2)0.25625 (16)0.0210 (3)
H11A−0.07100.23010.29330.031*
H11B−0.00220.02980.32790.031*
H11C−0.05980.13210.18190.031*
N10.21494 (18)0.17080 (16)0.20411 (12)0.0152 (3)
O10.56456 (16)0.12980 (14)0.24794 (11)0.0202 (2)
O20.30103 (17)−0.00587 (13)0.42939 (11)0.0212 (3)
O30.27313 (18)0.62312 (14)0.03808 (11)0.0220 (3)
H3A0.27850.6110−0.03920.033*
O40.26152 (18)0.46897 (16)−0.13289 (11)0.0264 (3)
S10.36145 (5)0.13574 (4)0.31790 (3)0.01424 (12)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
C10.0111 (6)0.0140 (7)0.0157 (7)−0.0025 (5)−0.0013 (5)−0.0046 (5)
C20.0141 (7)0.0192 (7)0.0154 (7)−0.0029 (6)−0.0034 (5)−0.0033 (6)
C30.0167 (7)0.0257 (8)0.0181 (7)−0.0037 (6)−0.0031 (6)−0.0101 (6)
C40.0189 (7)0.0187 (8)0.0251 (8)−0.0044 (6)−0.0014 (6)−0.0107 (6)
C50.0181 (7)0.0145 (7)0.0205 (7)−0.0024 (5)−0.0011 (6)−0.0032 (6)
C60.0128 (7)0.0160 (7)0.0148 (7)−0.0026 (5)−0.0010 (5)−0.0034 (5)
C70.0120 (7)0.0171 (7)0.0132 (7)0.0003 (5)−0.0008 (5)−0.0009 (5)
C80.0135 (7)0.0193 (7)0.0129 (7)0.0005 (5)−0.0023 (5)−0.0037 (5)
C90.0164 (7)0.0277 (8)0.0176 (7)0.0039 (6)−0.0049 (6)−0.0092 (6)
C100.0463 (11)0.0342 (10)0.0245 (9)0.0043 (8)−0.0133 (8)−0.0164 (7)
C110.0152 (7)0.0230 (8)0.0249 (8)−0.0049 (6)−0.0035 (6)−0.0056 (6)
N10.0144 (6)0.0165 (6)0.0157 (6)−0.0018 (5)−0.0045 (5)−0.0050 (5)
O10.0138 (5)0.0234 (6)0.0246 (6)0.0025 (4)−0.0036 (4)−0.0108 (5)
O20.0292 (6)0.0133 (5)0.0202 (5)−0.0044 (4)−0.0086 (5)0.0005 (4)
O30.0287 (6)0.0182 (6)0.0143 (5)−0.0019 (5)−0.0022 (5)0.0009 (4)
O40.0300 (6)0.0322 (7)0.0140 (5)0.0020 (5)−0.0058 (5)−0.0038 (5)
S10.01453 (19)0.01270 (19)0.01608 (19)0.00015 (13)−0.00467 (13)−0.00442 (13)

Geometric parameters (Å, °)

C1—C21.387 (2)C8—C91.448 (2)
C1—C61.404 (2)C9—O41.251 (2)
C1—S11.7580 (14)C9—C101.501 (2)
C2—C31.394 (2)C10—H10A0.9800
C2—H20.9500C10—H10B0.9800
C3—C41.388 (2)C10—H10C0.9800
C3—H30.9500C11—N11.4864 (19)
C4—C51.391 (2)C11—H11A0.9800
C4—H40.9500C11—H11B0.9800
C5—C61.397 (2)C11—H11C0.9800
C5—H50.9500N1—S11.6438 (12)
C6—C71.471 (2)O1—S11.4319 (11)
C7—O31.3316 (17)O2—S11.4314 (11)
C7—C81.378 (2)O3—H3A0.8400
C8—N11.4430 (18)
C2—C1—C6122.15 (13)O4—C9—C10119.76 (14)
C2—C1—S1120.70 (11)C8—C9—C10120.31 (15)
C6—C1—S1117.13 (11)C9—C10—H10A109.5
C1—C2—C3118.54 (14)C9—C10—H10B109.5
C1—C2—H2120.7H10A—C10—H10B109.5
C3—C2—H2120.7C9—C10—H10C109.5
C4—C3—C2120.14 (14)H10A—C10—H10C109.5
C4—C3—H3119.9H10B—C10—H10C109.5
C2—C3—H3119.9N1—C11—H11A109.5
C3—C4—C5121.04 (14)N1—C11—H11B109.5
C3—C4—H4119.5H11A—C11—H11B109.5
C5—C4—H4119.5N1—C11—H11C109.5
C4—C5—C6119.79 (14)H11A—C11—H11C109.5
C4—C5—H5120.1H11B—C11—H11C109.5
C6—C5—H5120.1C8—N1—C11114.26 (11)
C5—C6—C1118.30 (13)C8—N1—S1112.75 (10)
C5—C6—C7121.47 (13)C11—N1—S1116.79 (10)
C1—C6—C7120.23 (13)C7—O3—H3A109.5
O3—C7—C8122.30 (13)O2—S1—O1119.39 (7)
O3—C7—C6114.96 (13)O2—S1—N1108.47 (7)
C8—C7—C6122.73 (13)O1—S1—N1107.24 (6)
C7—C8—N1120.44 (12)O2—S1—C1109.27 (7)
C7—C8—C9120.64 (14)O1—S1—C1108.93 (7)
N1—C8—C9118.91 (13)N1—S1—C1102.15 (6)
O4—C9—C8119.92 (14)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O3—H3A···O40.841.782.525 (2)146
C4—H4···O2i0.952.363.193 (2)146

Symmetry codes: (i) x, y+1, z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: PV2072).

References

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