Acta Cryst. (2010). E66, o1070 [ doi:10.1107/S1600536810012365 ]
In the title compound, C12H13NO5S, the thiazine ring adopts a half chair conformation and an intramolecular O-H
O hydrogen bond generates an S(6) ring. In the crystal, the molecules are linked by C-HO interactions, leading to zigzag chains along the b axis.
Ethyl iodide (250 mg, 1.6 mmol) was added drop wise to the mixture of methyl 4-hydroxy-2H-1,2-benzothiazine-3-carboxylate-1,1-dioxide (350 mg, 1.37 mmol), anhydrous potassium carbonate (161 mg, 1.6 mmol) and dimethylformamide (5 ml) in a round bottom flask. Contents were stirred at room temperature for 5 h under nitrogen atmosphere and poured over ice cooled water (100 ml) resulting white precipetates, which was filtered and washed with cold water. Colourless needles of (I) were obtained by re-crystallization from a methanol solution under slow evaporation.
Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and PLATON (Spek, 2009); software used to prepare material for publication: X-SEED (Barbur, 2001); WinGX (Farrugia, 1999) and PLATON (Spek, 2009).
![[Figure 1]](./hb5390fig1thm.gif)
| Fig. 1. The molecular structure of (I) showing 50% displacement ellipsoids. |
![[Figure 2]](./hb5390fig2thm.gif)
| Fig. 2. Unit cell packing for (I) showing the inter and intramolecular hydrogen bondings using dashed lines. Hydrogen atoms have been omitted for clarity. |
| C12H13NO5S | F(000) = 592 |
| Mr = 283.29 | Dx = 1.475 Mg m−3 |
| Orthorhombic, Pna21 | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: P 2c -2n | Cell parameters from 733 reflections |
| a = 7.2460 (6) Å | θ = 2.6–17.3° |
| b = 20.548 (2) Å | µ = 0.27 mm−1 |
| c = 8.5710 (8) Å | T = 296 K |
| V = 1276.1 (2) Å3 | Cut needle, colourless |
| Z = 4 | 0.24 × 0.14 × 0.10 mm |
| Bruker KAPPA APEXII CCD diffractometer | 3148 independent reflections |
| Radiation source: fine-focus sealed tube | 1270 reflections with I > 2σ(I) |
| graphite | Rint = 0.133 |
| φ and ω scans | θmax = 28.3°, θmin = 2.0° |
| Absorption correction: multi-scan (SADABS; Bruker, 2007) | h = −9→9 |
| Tmin = 0.938, Tmax = 0.974 | k = −26→27 |
| 14253 measured reflections | l = −11→11 |
| Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
| Least-squares matrix: full | H-atom parameters constrained |
| R[F2 > 2σ(F2)] = 0.054 | w = 1/[σ2(Fo2) + (0.0219P)2] where P = (Fo2 + 2Fc2)/3 |
| wR(F2) = 0.102 | (Δ/σ)max < 0.001 |
| S = 0.95 | Δρmax = 0.22 e Å−3 |
| 3148 reflections | Δρmin = −0.25 e Å−3 |
| 176 parameters | Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
| 1 restraint | Extinction coefficient: 0.0062 (9) |
| Primary atom site location: structure-invariant direct methods | Absolute structure: Flack (1983), 1464 Friedel pairs |
| Secondary atom site location: difference Fourier map | Flack parameter: 0.07 (12) |
| C12H13NO5S | V = 1276.1 (2) Å3 |
| Mr = 283.29 | Z = 4 |
| Orthorhombic, Pna21 | Mo Kα radiation |
| a = 7.2460 (6) Å | µ = 0.27 mm−1 |
| b = 20.548 (2) Å | T = 296 K |
| c = 8.5710 (8) Å | 0.24 × 0.14 × 0.10 mm |
| Bruker KAPPA APEXII CCD diffractometer | 3148 independent reflections |
| Absorption correction: multi-scan (SADABS; Bruker, 2007) | 1270 reflections with I > 2σ(I) |
| Tmin = 0.938, Tmax = 0.974 | Rint = 0.133 |
| 14253 measured reflections | θmax = 28.3° |
| R[F2 > 2σ(F2)] = 0.054 | H-atom parameters constrained |
| wR(F2) = 0.102 | Δρmax = 0.22 e Å−3 |
| S = 0.95 | Δρmin = −0.25 e Å−3 |
| 3148 reflections | Absolute structure: Flack (1983), 1464 Friedel pairs |
| 176 parameters | Flack parameter: 0.07 (12) |
| 1 restraint |
Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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 | 0.19292 (16) | 0.06952 (6) | 0.49242 (15) | 0.0514 (4) | |
| O1 | 0.0578 (4) | 0.10023 (16) | 0.3936 (4) | 0.0648 (10) | |
| O2 | 0.1809 (4) | 0.00107 (13) | 0.5198 (4) | 0.0716 (10) | |
| O3 | 0.3931 (4) | 0.26033 (12) | 0.5272 (4) | 0.0532 (8) | |
| H3 | 0.4444 | 0.2709 | 0.4458 | 0.080* | |
| O4 | 0.5638 (4) | 0.23848 (15) | 0.2618 (4) | 0.0563 (10) | |
| O5 | 0.5818 (4) | 0.13380 (14) | 0.1843 (4) | 0.0550 (9) | |
| N1 | 0.3974 (4) | 0.08716 (17) | 0.4241 (4) | 0.0413 (9) | |
| C1 | 0.1976 (6) | 0.1103 (2) | 0.6695 (5) | 0.0422 (11) | |
| C2 | 0.1285 (6) | 0.0824 (2) | 0.8054 (6) | 0.0536 (14) | |
| H2 | 0.0732 | 0.0416 | 0.8027 | 0.064* | |
| C3 | 0.1429 (6) | 0.1160 (3) | 0.9446 (6) | 0.0560 (15) | |
| H3A | 0.1030 | 0.0970 | 1.0370 | 0.067* | |
| C4 | 0.2163 (6) | 0.1776 (2) | 0.9459 (5) | 0.0589 (15) | |
| H4 | 0.2201 | 0.2009 | 1.0389 | 0.071* | |
| C5 | 0.2849 (6) | 0.2056 (2) | 0.8105 (6) | 0.0560 (14) | |
| H5 | 0.3341 | 0.2474 | 0.8139 | 0.067* | |
| C6 | 0.2811 (6) | 0.1722 (2) | 0.6708 (6) | 0.0396 (11) | |
| C7 | 0.3701 (5) | 0.1955 (2) | 0.5296 (6) | 0.0406 (11) | |
| C8 | 0.4294 (6) | 0.1557 (2) | 0.4160 (5) | 0.0372 (11) | |
| C9 | 0.5296 (6) | 0.1805 (3) | 0.2822 (5) | 0.0471 (12) | |
| C10 | 0.6951 (6) | 0.1538 (2) | 0.0543 (5) | 0.0707 (16) | |
| H10A | 0.6288 | 0.1848 | −0.0079 | 0.106* | |
| H10B | 0.7252 | 0.1165 | −0.0083 | 0.106* | |
| H10C | 0.8066 | 0.1733 | 0.0926 | 0.106* | |
| C11 | 0.5572 (6) | 0.0441 (2) | 0.4634 (5) | 0.0548 (15) | |
| H11A | 0.6478 | 0.0475 | 0.3805 | 0.066* | |
| H11B | 0.5143 | −0.0006 | 0.4657 | 0.066* | |
| C12 | 0.6504 (6) | 0.0588 (3) | 0.6154 (7) | 0.0840 (19) | |
| H12A | 0.6928 | 0.1031 | 0.6152 | 0.126* | |
| H12B | 0.7537 | 0.0301 | 0.6290 | 0.126* | |
| H12C | 0.5646 | 0.0527 | 0.6994 | 0.126* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| S1 | 0.0554 (7) | 0.0474 (7) | 0.0516 (7) | −0.0144 (7) | 0.0019 (9) | −0.0055 (8) |
| O1 | 0.051 (2) | 0.083 (3) | 0.060 (2) | −0.0095 (18) | −0.010 (2) | −0.003 (2) |
| O2 | 0.097 (2) | 0.0399 (19) | 0.078 (3) | −0.0283 (16) | 0.014 (2) | −0.010 (2) |
| O3 | 0.065 (2) | 0.033 (2) | 0.061 (3) | −0.0045 (14) | 0.0097 (19) | 0.0007 (19) |
| O4 | 0.067 (2) | 0.042 (2) | 0.059 (2) | −0.0064 (17) | 0.0121 (19) | 0.0070 (18) |
| O5 | 0.068 (2) | 0.048 (2) | 0.050 (2) | 0.0000 (17) | 0.0208 (19) | −0.0001 (19) |
| N1 | 0.044 (2) | 0.037 (2) | 0.043 (2) | −0.0036 (17) | 0.0052 (18) | −0.0020 (18) |
| C1 | 0.038 (3) | 0.048 (3) | 0.040 (3) | 0.000 (2) | 0.000 (2) | −0.006 (3) |
| C2 | 0.038 (3) | 0.056 (4) | 0.066 (4) | −0.003 (2) | 0.009 (3) | 0.005 (3) |
| C3 | 0.056 (3) | 0.062 (4) | 0.050 (4) | 0.010 (3) | 0.012 (3) | 0.008 (3) |
| C4 | 0.062 (3) | 0.075 (4) | 0.039 (4) | 0.017 (3) | 0.006 (3) | −0.010 (3) |
| C5 | 0.061 (3) | 0.051 (3) | 0.056 (4) | 0.002 (3) | 0.003 (3) | −0.011 (3) |
| C6 | 0.039 (3) | 0.035 (3) | 0.045 (3) | 0.002 (2) | −0.001 (3) | 0.000 (3) |
| C7 | 0.044 (3) | 0.033 (3) | 0.045 (3) | −0.005 (2) | −0.003 (2) | −0.001 (3) |
| C8 | 0.040 (3) | 0.027 (3) | 0.045 (3) | −0.004 (2) | −0.005 (2) | 0.002 (2) |
| C9 | 0.043 (3) | 0.058 (3) | 0.040 (3) | −0.003 (3) | −0.006 (3) | −0.001 (3) |
| C10 | 0.086 (4) | 0.065 (4) | 0.061 (4) | −0.004 (3) | 0.036 (3) | 0.002 (3) |
| C11 | 0.057 (3) | 0.037 (3) | 0.070 (4) | 0.010 (2) | 0.005 (3) | 0.010 (3) |
| C12 | 0.069 (4) | 0.102 (5) | 0.081 (5) | 0.019 (3) | −0.013 (3) | 0.015 (4) |
| S1—O2 | 1.429 (3) | C4—C5 | 1.388 (6) |
| S1—O1 | 1.441 (3) | C4—H4 | 0.9300 |
| S1—N1 | 1.634 (3) | C5—C6 | 1.381 (6) |
| S1—C1 | 1.734 (5) | C5—H5 | 0.9300 |
| O3—C7 | 1.343 (4) | C6—C7 | 1.452 (6) |
| O3—H3 | 0.8200 | C7—C8 | 1.343 (5) |
| O4—C9 | 1.229 (5) | C8—C9 | 1.450 (6) |
| O5—C9 | 1.330 (5) | C10—H10A | 0.9600 |
| O5—C10 | 1.444 (5) | C10—H10B | 0.9600 |
| N1—C8 | 1.428 (5) | C10—H10C | 0.9600 |
| N1—C11 | 1.495 (5) | C11—C12 | 1.499 (6) |
| C1—C2 | 1.392 (6) | C11—H11A | 0.9700 |
| C1—C6 | 1.408 (5) | C11—H11B | 0.9700 |
| C2—C3 | 1.383 (6) | C12—H12A | 0.9600 |
| C2—H2 | 0.9300 | C12—H12B | 0.9600 |
| C3—C4 | 1.372 (6) | C12—H12C | 0.9600 |
| C3—H3A | 0.9300 | ||
| O2—S1—O1 | 119.1 (2) | C1—C6—C7 | 118.8 (4) |
| O2—S1—N1 | 109.44 (18) | C8—C7—O3 | 123.6 (4) |
| O1—S1—N1 | 107.97 (19) | C8—C7—C6 | 123.0 (4) |
| O2—S1—C1 | 109.4 (2) | O3—C7—C6 | 113.3 (4) |
| O1—S1—C1 | 108.4 (2) | C7—C8—N1 | 120.9 (4) |
| N1—S1—C1 | 100.9 (2) | C7—C8—C9 | 121.3 (4) |
| C7—O3—H3 | 109.5 | N1—C8—C9 | 117.9 (4) |
| C9—O5—C10 | 116.3 (3) | O4—C9—O5 | 123.6 (4) |
| C8—N1—C11 | 117.9 (3) | O4—C9—C8 | 123.7 (4) |
| C8—N1—S1 | 112.5 (3) | O5—C9—C8 | 112.7 (4) |
| C11—N1—S1 | 119.4 (3) | O5—C10—H10A | 109.5 |
| C2—C1—C6 | 121.3 (4) | O5—C10—H10B | 109.5 |
| C2—C1—S1 | 121.8 (4) | H10A—C10—H10B | 109.5 |
| C6—C1—S1 | 116.9 (4) | O5—C10—H10C | 109.5 |
| C3—C2—C1 | 119.3 (4) | H10A—C10—H10C | 109.5 |
| C3—C2—H2 | 120.4 | H10B—C10—H10C | 109.5 |
| C1—C2—H2 | 120.4 | N1—C11—C12 | 115.2 (4) |
| C4—C3—C2 | 119.8 (5) | N1—C11—H11A | 108.5 |
| C4—C3—H3A | 120.1 | C12—C11—H11A | 108.5 |
| C2—C3—H3A | 120.1 | N1—C11—H11B | 108.5 |
| C3—C4—C5 | 120.9 (4) | C12—C11—H11B | 108.5 |
| C3—C4—H4 | 119.5 | H11A—C11—H11B | 107.5 |
| C5—C4—H4 | 119.5 | C11—C12—H12A | 109.5 |
| C6—C5—C4 | 120.8 (4) | C11—C12—H12B | 109.5 |
| C6—C5—H5 | 119.6 | H12A—C12—H12B | 109.5 |
| C4—C5—H5 | 119.6 | C11—C12—H12C | 109.5 |
| C5—C6—C1 | 117.7 (4) | H12A—C12—H12C | 109.5 |
| C5—C6—C7 | 123.3 (4) | H12B—C12—H12C | 109.5 |
| O2—S1—N1—C8 | −171.2 (3) | S1—C1—C6—C7 | −4.9 (5) |
| O1—S1—N1—C8 | 57.8 (3) | C5—C6—C7—C8 | 153.4 (4) |
| C1—S1—N1—C8 | −55.9 (3) | C1—C6—C7—C8 | −21.9 (6) |
| O2—S1—N1—C11 | −26.6 (4) | C5—C6—C7—O3 | −24.2 (6) |
| O1—S1—N1—C11 | −157.6 (3) | C1—C6—C7—O3 | 160.5 (4) |
| C1—S1—N1—C11 | 88.7 (3) | O3—C7—C8—N1 | −178.8 (4) |
| O2—S1—C1—C2 | −22.5 (4) | C6—C7—C8—N1 | 3.8 (6) |
| O1—S1—C1—C2 | 108.9 (4) | O3—C7—C8—C9 | 2.0 (6) |
| N1—S1—C1—C2 | −137.8 (4) | C6—C7—C8—C9 | −175.4 (4) |
| O2—S1—C1—C6 | 155.2 (3) | C11—N1—C8—C7 | −105.7 (4) |
| O1—S1—C1—C6 | −73.4 (4) | S1—N1—C8—C7 | 39.5 (5) |
| N1—S1—C1—C6 | 39.9 (4) | C11—N1—C8—C9 | 73.6 (5) |
| C6—C1—C2—C3 | −0.3 (7) | S1—N1—C8—C9 | −141.2 (3) |
| S1—C1—C2—C3 | 177.3 (3) | C10—O5—C9—O4 | 4.3 (7) |
| C1—C2—C3—C4 | 3.3 (7) | C10—O5—C9—C8 | −175.3 (4) |
| C2—C3—C4—C5 | −3.2 (7) | C7—C8—C9—O4 | −1.5 (7) |
| C3—C4—C5—C6 | 0.0 (7) | N1—C8—C9—O4 | 179.3 (4) |
| C4—C5—C6—C1 | 2.9 (6) | C7—C8—C9—O5 | 178.1 (4) |
| C4—C5—C6—C7 | −172.4 (4) | N1—C8—C9—O5 | −1.1 (5) |
| C2—C1—C6—C5 | −2.8 (6) | C8—N1—C11—C12 | 57.6 (5) |
| S1—C1—C6—C5 | 179.5 (3) | S1—N1—C11—C12 | −85.1 (4) |
| C2—C1—C6—C7 | 172.8 (4) |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O3—H3···O4 | 0.82 | 1.92 | 2.628 (5) | 144 |
| C4—H4···O4i | 0.93 | 2.55 | 3.395 (5) | 152 |
| C10—H10B···O2ii | 0.96 | 2.52 | 3.320 (5) | 141 |
| Symmetry codes: (i) x−1/2, −y+1/2, z+1; (ii) −x+1, −y, z−1/2. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O3—H3···O4 | 0.82 | 1.92 | 2.628 (5) | 144 |
| C4—H4···O4i | 0.93 | 2.55 | 3.395 (5) | 152 |
| C10—H10B···O2ii | 0.96 | 2.52 | 3.320 (5) | 141 |
| Symmetry codes: (i) x−1/2, −y+1/2, z+1; (ii) −x+1, −y, z−1/2. |
The authors acknowledge the Higher Education Commission (HEC) of Pakistan for providing a grant under the project `Strengthening the Materials Chemistry Laboratory at GC University, Lahore'. MNA also acknowledges the HEC for providing a fellowship under the International Research Support Initiative Program (IRSIP)
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Under the heading of synthesis and X-ray studies and biological evaluation of thiazine related heterocycles our group has already reported biological applications (Zia-ur-Rehman et al., 2005, 2006) and the crystal structures of 1,2-benzothiazine derivatives (Arshad et al., 2009a,b) II & III. The title compound Methyl 2-ethyl-4-hydroxy-2H-1,2-benzothiazine-3-carboxylate 1,1-dioxide (I) is different only in H-alkylation. The hydrogen bonding interactions in I, II and III are pretty much common. The intramolecular O–H···O interaction tend to rise the six membered ring motif R11(6) (Bernstein, et al., 1995) which is almost planar with the r.m.s deviaton of 0.0156Å and iclined at dihedral angle of 25.1 (6)° & 17.5 (6)° with respect to the thiazine and benzene ring respectively. The half chair shaped thiazine ring exihibits a maximum deviation from the least square plane measure 0.347 (2)Å for S1 and 0.345 (2)Å for C1. The intermoleculear C–H···O hydrogen bonding forms zig-zag network along the b axes. The bond lngths and bond angles are compareable with the molecules II and III.