organic compounds
Ethyl 2-(3,4-dimethyl-5,5-dioxo-1H,4H-benzo[e]pyrazolo[4,3-c][1,2]thiazin-1-yl)acetate
aInstitute of Chemistry, University of the Punjab, Lahore 54590, Pakistan, bDepartment of Chemistry, Government College University, Faisalabad 38000, Pakistan, cApplied Chemistry Research Center, PCSIR Laboratories Complex, Lahore 54600, Pakistan, and dDepartment of Chemistry, University of Calgary, 2500 University Drive NW, Calgary, Alberta, Canada T2N 1N4
*Correspondence e-mail: matloob_123@yahoo.com
In the title molecule, C15H17N3O4S, the heterocyclic thiazine ring adopts a twist-boat conformation, which differs from that in related compounds, with adjacent S and C atoms displaced by 0.981 (4) and 0.413 (5) Å, respectively, on the same side of the mean plane formed by the remaining ring atoms. The mean plane of the benzene ring makes a dihedral angle of 23.43 (14)° with the mean plane of the pyrazole ring. In the crystal, molecules are connected by weak C—H⋯O hydrogen bonds to form a three-dimensional network. The H atoms of the methyl group attached to the pyrazole ring were refined over six sites with equal occupancies.
Related literature
For background literature and crystal structures of related pyrazolobenzothiazine derivatives, see: Aslam et al. (2012); Ahmad et al. (2012). For the Cambridge Structural Database, see: Allen (2002).
Experimental
Crystal data
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Refinement
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Data collection: COLLECT (Nonius, 1998); cell DENZO (Otwinowski & Minor, 1997); data reduction: SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97.
Supporting information
https://doi.org/10.1107/S1600536812039797/lh5533sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812039797/lh5533Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S1600536812039797/lh5533Isup3.cml
A mixture of 3,4-dimethyl-2,4-dihydropyrazolo[4,3-c][1,2]benzothiazine 5,5-dioxide (5.0 g, 0.020 moles), anhydrous potassium carbonate (3.31 g, 0.024 moles), ethyl chloroacetate (2.94 g, 0.024 moles) and acetonitrile (30 ml) was refluxed for 10 h followed by the removal of solvent under vacuum. The residue obtained was washed with cold water to get the title compound as a white crystalline product. Transparent crystals suitable for X-ray crystallographic studies were grown from a CHCl3 solution at room temperature by slow evaporation.
All H atoms were positioned geometrically and refined using a riding model, with C—H = 0.95–0.99 Å and Uiso(H) = 1.2Ueq(C) or 1.5Ueq(Cmethyl).
Continuing our research on hybrid pyrazolobenzothiazine derivatives based on pyrazole and benzothiazine nuclei which are well known for their wide range of biological activities (Ahmad et al., 2012) we have synthsized the title compound which is a novel product wherein the ethylecatate has been substituted at N1 of the pyrazole ring instead of the usual N2 position. A search of the Cambridge Structural Database (Allen, 2002; CSD Version 5.33) revealed eleven structures with substituents at the N2 position and only one structure with substituents at both N1 and N2 positions and no pyrazolobenzothiazine derivative with a substituent at the N1 position. We report the synthesis and
of the title compound in this article.The bond distances and angles in the title compound (Fig. 1) agree very well with those reported in closely related structures (Aslam et al., 2012; Ahmad et al., 2012). The heterocyclic thiazine ring adopts a twist-boat conformation with atoms S1 and C1 displaced by 0.981 (4) and 0.413 (5) Å, respectively, on the same side from the mean plane formed by the remaining ring atoms (N1/C6–C8 atoms). The mean-plane of the benzene ring C1–C6 makes a dihedral angle 23.43 (14)° with the mean-plane of the pyrazole ring (N2/N3/C7/C8/C9). The acetate group (O3/O4/C12/C13/C14) is essentially planar (rmsd 0.031 Å) and its mean-plane is oriented at 82.4 (2)° with respect to the pyrazole ring.
The
is stabilized by weak intermolecular C—H···O hydrogen bonds resulting in a three-dimensional network (Fig. 2 and Table 1).For background literature and crystal structures of related pyrazolobenzothiazine derivatives, see: Aslam et al. (2012); Ahmad et al. (2012). For the Cambridge Structural Database, see: Allen (2002).
Data collection: COLLECT (Nonius, 1998); cell
DENZO (Otwinowski & Minor, 1997); data reduction: SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).Fig. 1. The molecular structure of the title compound with displacement ellipsoids drawn at the 30% probability level. H atoms are presented as small spheres of an arbitrary radius. | |
Fig. 2. The weak hydrogen bonds (dashed lines) in the crystal structure of the title compound. H atoms non-participating in hydrogen bonds are omitted for clarity. |
C15H17N3O4S | F(000) = 704 |
Mr = 335.38 | Dx = 1.398 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 3460 reflections |
a = 8.3027 (2) Å | θ = 1.0–27.5° |
b = 8.5915 (3) Å | µ = 0.23 mm−1 |
c = 22.3476 (7) Å | T = 173 K |
β = 90.674 (2)° | Block, colourless |
V = 1594.00 (8) Å3 | 0.20 × 0.18 × 0.16 mm |
Z = 4 |
Nonius KappaCCD diffractometer | 3576 independent reflections |
Radiation source: fine-focus sealed tube | 2820 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.039 |
ω and φ scans | θmax = 27.5°, θmin = 3.0° |
Absorption correction: multi-scan (SORTAV; Blessing, 1997) | h = −10→10 |
Tmin = 0.956, Tmax = 0.965 | k = −11→11 |
15091 measured reflections | l = −28→28 |
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)] = 0.056 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.127 | H-atom parameters constrained |
S = 1.10 | w = 1/[σ2(Fo2) + (0.0235P)2 + 2.7353P] where P = (Fo2 + 2Fc2)/3 |
3576 reflections | (Δ/σ)max < 0.001 |
210 parameters | Δρmax = 0.33 e Å−3 |
0 restraints | Δρmin = −0.45 e Å−3 |
C15H17N3O4S | V = 1594.00 (8) Å3 |
Mr = 335.38 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 8.3027 (2) Å | µ = 0.23 mm−1 |
b = 8.5915 (3) Å | T = 173 K |
c = 22.3476 (7) Å | 0.20 × 0.18 × 0.16 mm |
β = 90.674 (2)° |
Nonius KappaCCD diffractometer | 3576 independent reflections |
Absorption correction: multi-scan (SORTAV; Blessing, 1997) | 2820 reflections with I > 2σ(I) |
Tmin = 0.956, Tmax = 0.965 | Rint = 0.039 |
15091 measured reflections |
R[F2 > 2σ(F2)] = 0.056 | 0 restraints |
wR(F2) = 0.127 | H-atom parameters constrained |
S = 1.10 | Δρmax = 0.33 e Å−3 |
3576 reflections | Δρmin = −0.45 e Å−3 |
210 parameters |
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. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
S1 | 0.60768 (7) | 0.28409 (8) | 0.67513 (3) | 0.02293 (16) | |
O1 | 0.6208 (2) | 0.4498 (2) | 0.67696 (8) | 0.0301 (4) | |
O2 | 0.7203 (2) | 0.1922 (2) | 0.70884 (8) | 0.0295 (4) | |
O3 | 0.1309 (3) | −0.4262 (3) | 0.64119 (9) | 0.0435 (6) | |
O4 | 0.1716 (3) | −0.2669 (3) | 0.56356 (10) | 0.0537 (7) | |
N1 | 0.6194 (2) | 0.2279 (3) | 0.60491 (9) | 0.0233 (5) | |
N2 | 0.4504 (3) | −0.1506 (3) | 0.61898 (9) | 0.0251 (5) | |
N3 | 0.5677 (3) | −0.1867 (3) | 0.57904 (10) | 0.0296 (5) | |
C1 | 0.4117 (3) | 0.2290 (3) | 0.69663 (11) | 0.0231 (5) | |
C2 | 0.3265 (3) | 0.3239 (3) | 0.73520 (12) | 0.0289 (6) | |
H2 | 0.3708 | 0.4194 | 0.7490 | 0.035* | |
C3 | 0.1753 (3) | 0.2761 (4) | 0.75310 (13) | 0.0365 (7) | |
H3 | 0.1166 | 0.3378 | 0.7806 | 0.044* | |
C4 | 0.1088 (3) | 0.1396 (4) | 0.73138 (13) | 0.0352 (7) | |
H4 | 0.0046 | 0.1088 | 0.7438 | 0.042* | |
C5 | 0.1925 (3) | 0.0476 (3) | 0.69173 (12) | 0.0300 (6) | |
H5 | 0.1438 | −0.0440 | 0.6760 | 0.036* | |
C6 | 0.3483 (3) | 0.0884 (3) | 0.67452 (11) | 0.0237 (5) | |
C7 | 0.4492 (3) | 0.0034 (3) | 0.63269 (11) | 0.0230 (5) | |
C8 | 0.5724 (3) | 0.0676 (3) | 0.59991 (11) | 0.0231 (5) | |
C9 | 0.6426 (3) | −0.0531 (3) | 0.56744 (11) | 0.0273 (6) | |
C10 | 0.7810 (4) | −0.0464 (4) | 0.52519 (14) | 0.0400 (7) | |
H10A | 0.8020 | −0.1507 | 0.5094 | 0.060* | 0.50 |
H10B | 0.8771 | −0.0083 | 0.5465 | 0.060* | 0.50 |
H10C | 0.7547 | 0.0243 | 0.4921 | 0.060* | 0.50 |
H10D | 0.8205 | 0.0609 | 0.5226 | 0.060* | 0.50 |
H10E | 0.7454 | −0.0815 | 0.4855 | 0.060* | 0.50 |
H10F | 0.8679 | −0.1141 | 0.5399 | 0.060* | 0.50 |
C11 | 0.5531 (4) | 0.3344 (3) | 0.55871 (12) | 0.0354 (7) | |
H11A | 0.5831 | 0.2970 | 0.5189 | 0.053* | |
H11B | 0.5968 | 0.4391 | 0.5650 | 0.053* | |
H11C | 0.4355 | 0.3375 | 0.5616 | 0.053* | |
C12 | 0.3618 (3) | −0.2766 (3) | 0.64581 (11) | 0.0268 (6) | |
H12A | 0.3318 | −0.2465 | 0.6870 | 0.032* | |
H12B | 0.4325 | −0.3692 | 0.6487 | 0.032* | |
C13 | 0.2108 (3) | −0.3195 (3) | 0.61103 (12) | 0.0289 (6) | |
C14 | −0.0120 (4) | −0.4933 (5) | 0.61234 (15) | 0.0498 (9) | |
H14A | −0.0681 | −0.4125 | 0.5884 | 0.060* | |
H14B | −0.0871 | −0.5311 | 0.6432 | 0.060* | |
C15 | 0.0347 (4) | −0.6243 (4) | 0.57295 (16) | 0.0516 (9) | |
H15A | −0.0622 | −0.6712 | 0.5552 | 0.077* | |
H15B | 0.0930 | −0.7027 | 0.5966 | 0.077* | |
H15C | 0.1042 | −0.5855 | 0.5411 | 0.077* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0218 (3) | 0.0242 (3) | 0.0228 (3) | −0.0016 (3) | 0.0000 (2) | −0.0012 (3) |
O1 | 0.0321 (10) | 0.0244 (10) | 0.0339 (10) | −0.0043 (8) | 0.0013 (8) | −0.0057 (8) |
O2 | 0.0242 (9) | 0.0367 (11) | 0.0276 (9) | 0.0017 (8) | −0.0034 (7) | 0.0017 (8) |
O3 | 0.0440 (12) | 0.0537 (15) | 0.0330 (11) | −0.0269 (11) | 0.0023 (9) | 0.0034 (10) |
O4 | 0.0597 (15) | 0.0542 (16) | 0.0466 (14) | −0.0224 (12) | −0.0224 (12) | 0.0196 (12) |
N1 | 0.0263 (11) | 0.0227 (11) | 0.0210 (10) | −0.0037 (9) | 0.0032 (8) | −0.0002 (9) |
N2 | 0.0313 (11) | 0.0237 (12) | 0.0204 (10) | −0.0042 (9) | 0.0045 (9) | −0.0025 (9) |
N3 | 0.0361 (12) | 0.0298 (13) | 0.0231 (11) | −0.0019 (10) | 0.0093 (9) | −0.0039 (10) |
C1 | 0.0232 (12) | 0.0264 (13) | 0.0198 (12) | 0.0043 (10) | 0.0011 (9) | 0.0015 (10) |
C2 | 0.0317 (14) | 0.0263 (15) | 0.0287 (14) | 0.0032 (11) | 0.0035 (11) | −0.0015 (11) |
C3 | 0.0338 (15) | 0.0379 (17) | 0.0381 (16) | 0.0142 (13) | 0.0132 (12) | 0.0002 (14) |
C4 | 0.0221 (13) | 0.0428 (18) | 0.0408 (16) | 0.0041 (12) | 0.0078 (11) | 0.0069 (14) |
C5 | 0.0249 (13) | 0.0311 (15) | 0.0342 (15) | −0.0011 (12) | 0.0007 (11) | 0.0007 (12) |
C6 | 0.0220 (12) | 0.0270 (14) | 0.0219 (12) | 0.0015 (10) | −0.0008 (10) | 0.0019 (10) |
C7 | 0.0234 (12) | 0.0256 (13) | 0.0200 (12) | −0.0018 (10) | −0.0012 (10) | −0.0006 (10) |
C8 | 0.0249 (12) | 0.0238 (13) | 0.0206 (12) | −0.0034 (10) | 0.0010 (10) | 0.0000 (10) |
C9 | 0.0327 (14) | 0.0275 (14) | 0.0217 (13) | −0.0016 (12) | 0.0066 (11) | −0.0007 (11) |
C10 | 0.0475 (18) | 0.0366 (17) | 0.0362 (16) | −0.0020 (14) | 0.0200 (14) | −0.0044 (14) |
C11 | 0.0515 (18) | 0.0303 (16) | 0.0244 (14) | −0.0047 (14) | −0.0019 (12) | 0.0074 (12) |
C12 | 0.0332 (14) | 0.0236 (13) | 0.0234 (13) | −0.0036 (11) | 0.0003 (11) | 0.0028 (11) |
C13 | 0.0323 (14) | 0.0284 (15) | 0.0260 (14) | −0.0043 (12) | 0.0016 (11) | −0.0004 (11) |
C14 | 0.0363 (17) | 0.063 (2) | 0.050 (2) | −0.0272 (17) | 0.0035 (15) | −0.0070 (18) |
C15 | 0.052 (2) | 0.047 (2) | 0.055 (2) | −0.0165 (17) | −0.0085 (17) | −0.0043 (18) |
S1—O1 | 1.429 (2) | C6—C7 | 1.458 (3) |
S1—O2 | 1.4312 (19) | C7—C8 | 1.381 (3) |
S1—N1 | 1.646 (2) | C8—C9 | 1.397 (4) |
S1—C1 | 1.767 (3) | C9—C10 | 1.497 (4) |
O3—C13 | 1.321 (3) | C10—H10A | 0.9800 |
O3—C14 | 1.462 (3) | C10—H10B | 0.9800 |
O4—C13 | 1.195 (3) | C10—H10C | 0.9800 |
N1—C8 | 1.435 (3) | C10—H10D | 0.9800 |
N1—C11 | 1.481 (3) | C10—H10E | 0.9800 |
N2—C7 | 1.358 (3) | C10—H10F | 0.9800 |
N2—N3 | 1.365 (3) | C11—H11A | 0.9800 |
N2—C12 | 1.443 (3) | C11—H11B | 0.9800 |
N3—C9 | 1.333 (3) | C11—H11C | 0.9800 |
C1—C2 | 1.387 (4) | C12—C13 | 1.513 (4) |
C1—C6 | 1.405 (4) | C12—H12A | 0.9900 |
C2—C3 | 1.384 (4) | C12—H12B | 0.9900 |
C2—H2 | 0.9500 | C14—C15 | 1.483 (5) |
C3—C4 | 1.381 (4) | C14—H14A | 0.9900 |
C3—H3 | 0.9500 | C14—H14B | 0.9900 |
C4—C5 | 1.381 (4) | C15—H15A | 0.9800 |
C4—H4 | 0.9500 | C15—H15B | 0.9800 |
C5—C6 | 1.399 (4) | C15—H15C | 0.9800 |
C5—H5 | 0.9500 | ||
O1—S1—O2 | 119.04 (12) | H10A—C10—H10C | 109.5 |
O1—S1—N1 | 108.32 (12) | H10B—C10—H10C | 109.5 |
O2—S1—N1 | 107.12 (11) | C9—C10—H10D | 109.5 |
O1—S1—C1 | 109.24 (12) | H10A—C10—H10D | 141.1 |
O2—S1—C1 | 107.91 (12) | H10B—C10—H10D | 56.3 |
N1—S1—C1 | 104.22 (11) | H10C—C10—H10D | 56.3 |
C13—O3—C14 | 117.3 (2) | C9—C10—H10E | 109.5 |
C8—N1—C11 | 116.1 (2) | H10A—C10—H10E | 56.3 |
C8—N1—S1 | 109.67 (17) | H10B—C10—H10E | 141.1 |
C11—N1—S1 | 117.25 (18) | H10C—C10—H10E | 56.3 |
C7—N2—N3 | 112.1 (2) | H10D—C10—H10E | 109.5 |
C7—N2—C12 | 129.2 (2) | C9—C10—H10F | 109.5 |
N3—N2—C12 | 118.2 (2) | H10A—C10—H10F | 56.3 |
C9—N3—N2 | 105.6 (2) | H10B—C10—H10F | 56.3 |
C2—C1—C6 | 122.2 (2) | H10C—C10—H10F | 141.1 |
C2—C1—S1 | 119.3 (2) | H10D—C10—H10F | 109.5 |
C6—C1—S1 | 118.50 (19) | H10E—C10—H10F | 109.5 |
C3—C2—C1 | 118.4 (3) | N1—C11—H11A | 109.5 |
C3—C2—H2 | 120.8 | N1—C11—H11B | 109.5 |
C1—C2—H2 | 120.8 | H11A—C11—H11B | 109.5 |
C4—C3—C2 | 120.7 (3) | N1—C11—H11C | 109.5 |
C4—C3—H3 | 119.7 | H11A—C11—H11C | 109.5 |
C2—C3—H3 | 119.7 | H11B—C11—H11C | 109.5 |
C5—C4—C3 | 120.6 (3) | N2—C12—C13 | 113.1 (2) |
C5—C4—H4 | 119.7 | N2—C12—H12A | 109.0 |
C3—C4—H4 | 119.7 | C13—C12—H12A | 109.0 |
C4—C5—C6 | 120.5 (3) | N2—C12—H12B | 109.0 |
C4—C5—H5 | 119.8 | C13—C12—H12B | 109.0 |
C6—C5—H5 | 119.8 | H12A—C12—H12B | 107.8 |
C5—C6—C1 | 117.5 (2) | O4—C13—O3 | 125.6 (3) |
C5—C6—C7 | 126.2 (2) | O4—C13—C12 | 125.4 (3) |
C1—C6—C7 | 116.1 (2) | O3—C13—C12 | 109.0 (2) |
N2—C7—C8 | 105.2 (2) | O3—C14—C15 | 110.2 (3) |
N2—C7—C6 | 129.7 (2) | O3—C14—H14A | 109.6 |
C8—C7—C6 | 125.1 (2) | C15—C14—H14A | 109.6 |
C7—C8—C9 | 107.2 (2) | O3—C14—H14B | 109.6 |
C7—C8—N1 | 123.0 (2) | C15—C14—H14B | 109.6 |
C9—C8—N1 | 129.6 (2) | H14A—C14—H14B | 108.1 |
N3—C9—C8 | 109.9 (2) | C14—C15—H15A | 109.5 |
N3—C9—C10 | 121.3 (3) | C14—C15—H15B | 109.5 |
C8—C9—C10 | 128.8 (3) | H15A—C15—H15B | 109.5 |
C9—C10—H10A | 109.5 | C14—C15—H15C | 109.5 |
C9—C10—H10B | 109.5 | H15A—C15—H15C | 109.5 |
H10A—C10—H10B | 109.5 | H15B—C15—H15C | 109.5 |
C9—C10—H10C | 109.5 | ||
O1—S1—N1—C8 | −167.65 (16) | N3—N2—C7—C6 | −177.6 (2) |
O2—S1—N1—C8 | 62.78 (19) | C12—N2—C7—C6 | −6.1 (4) |
C1—S1—N1—C8 | −51.42 (19) | C5—C6—C7—N2 | −27.8 (4) |
O1—S1—N1—C11 | −32.5 (2) | C1—C6—C7—N2 | 156.1 (3) |
O2—S1—N1—C11 | −162.02 (19) | C5—C6—C7—C8 | 155.4 (3) |
C1—S1—N1—C11 | 83.8 (2) | C1—C6—C7—C8 | −20.7 (4) |
C7—N2—N3—C9 | 0.2 (3) | N2—C7—C8—C9 | 0.2 (3) |
C12—N2—N3—C9 | −172.2 (2) | C6—C7—C8—C9 | 177.6 (2) |
O1—S1—C1—C2 | −28.1 (2) | N2—C7—C8—N1 | −175.4 (2) |
O2—S1—C1—C2 | 102.6 (2) | C6—C7—C8—N1 | 2.1 (4) |
N1—S1—C1—C2 | −143.7 (2) | C11—N1—C8—C7 | −98.0 (3) |
O1—S1—C1—C6 | 152.79 (19) | S1—N1—C8—C7 | 37.7 (3) |
O2—S1—C1—C6 | −76.4 (2) | C11—N1—C8—C9 | 87.5 (3) |
N1—S1—C1—C6 | 37.2 (2) | S1—N1—C8—C9 | −136.7 (3) |
C6—C1—C2—C3 | 1.2 (4) | N2—N3—C9—C8 | −0.1 (3) |
S1—C1—C2—C3 | −177.9 (2) | N2—N3—C9—C10 | 179.6 (2) |
C1—C2—C3—C4 | −2.2 (4) | C7—C8—C9—N3 | 0.0 (3) |
C2—C3—C4—C5 | 0.5 (4) | N1—C8—C9—N3 | 175.1 (2) |
C3—C4—C5—C6 | 2.3 (4) | C7—C8—C9—C10 | −179.7 (3) |
C4—C5—C6—C1 | −3.2 (4) | N1—C8—C9—C10 | −4.6 (5) |
C4—C5—C6—C7 | −179.2 (3) | C7—N2—C12—C13 | 97.8 (3) |
C2—C1—C6—C5 | 1.5 (4) | N3—N2—C12—C13 | −91.2 (3) |
S1—C1—C6—C5 | −179.50 (19) | C14—O3—C13—O4 | 4.4 (5) |
C2—C1—C6—C7 | 177.9 (2) | C14—O3—C13—C12 | −174.7 (3) |
S1—C1—C6—C7 | −3.1 (3) | N2—C12—C13—O4 | 6.1 (4) |
N3—N2—C7—C8 | −0.2 (3) | N2—C12—C13—O3 | −174.8 (2) |
C12—N2—C7—C8 | 171.2 (2) | C13—O3—C14—C15 | 85.1 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
C12—H12A···O2i | 0.99 | 2.43 | 3.338 (3) | 152 |
C12—H12B···O1ii | 0.99 | 2.29 | 3.255 (3) | 165 |
C4—H4···O2iii | 0.95 | 2.58 | 3.290 (3) | 132 |
C10—H10C···O4iv | 0.98 | 2.51 | 3.369 (4) | 147 |
C14—H14B···O1v | 0.99 | 2.55 | 3.424 (4) | 147 |
C11—H11B···O1 | 0.98 | 2.51 | 2.872 (3) | 102 |
Symmetry codes: (i) −x+1, y−1/2, −z+3/2; (ii) x, y−1, z; (iii) x−1, y, z; (iv) −x+1, −y, −z+1; (v) x−1, y−1, z. |
Experimental details
Crystal data | |
Chemical formula | C15H17N3O4S |
Mr | 335.38 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 173 |
a, b, c (Å) | 8.3027 (2), 8.5915 (3), 22.3476 (7) |
β (°) | 90.674 (2) |
V (Å3) | 1594.00 (8) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.23 |
Crystal size (mm) | 0.20 × 0.18 × 0.16 |
Data collection | |
Diffractometer | Nonius KappaCCD |
Absorption correction | Multi-scan (SORTAV; Blessing, 1997) |
Tmin, Tmax | 0.956, 0.965 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 15091, 3576, 2820 |
Rint | 0.039 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.056, 0.127, 1.10 |
No. of reflections | 3576 |
No. of parameters | 210 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.33, −0.45 |
Computer programs: COLLECT (Nonius, 1998), DENZO (Otwinowski & Minor, 1997), SCALEPACK (Otwinowski & Minor, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997).
D—H···A | D—H | H···A | D···A | D—H···A |
C12—H12A···O2i | 0.99 | 2.43 | 3.338 (3) | 152.0 |
C12—H12B···O1ii | 0.99 | 2.29 | 3.255 (3) | 165.1 |
C4—H4···O2iii | 0.95 | 2.58 | 3.290 (3) | 131.8 |
C10—H10C···O4iv | 0.98 | 2.51 | 3.369 (4) | 146.7 |
C14—H14B···O1v | 0.99 | 2.55 | 3.424 (4) | 146.6 |
Symmetry codes: (i) −x+1, y−1/2, −z+3/2; (ii) x, y−1, z; (iii) x−1, y, z; (iv) −x+1, −y, −z+1; (v) x−1, y−1, z. |
Acknowledgements
The authors are grateful to the Higher Education Commission, Pakistan, and the Institute of Chemistry, University of the Punjab, Lahore, Pakistan, for financial support.
References
Ahmad, M., Siddiqui, H. L., Ahmad, N., Aslam, S. & Parvez, M. (2012). Acta Cryst. E68, o2470–o2471. CSD CrossRef IUCr Journals Google Scholar
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This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
Continuing our research on hybrid pyrazolobenzothiazine derivatives based on pyrazole and benzothiazine nuclei which are well known for their wide range of biological activities (Ahmad et al., 2012) we have synthsized the title compound which is a novel product wherein the ethylecatate has been substituted at N1 of the pyrazole ring instead of the usual N2 position. A search of the Cambridge Structural Database (Allen, 2002; CSD Version 5.33) revealed eleven structures with substituents at the N2 position and only one structure with substituents at both N1 and N2 positions and no pyrazolobenzothiazine derivative with a substituent at the N1 position. We report the synthesis and crystal structure of the title compound in this article.
The bond distances and angles in the title compound (Fig. 1) agree very well with those reported in closely related structures (Aslam et al., 2012; Ahmad et al., 2012). The heterocyclic thiazine ring adopts a twist-boat conformation with atoms S1 and C1 displaced by 0.981 (4) and 0.413 (5) Å, respectively, on the same side from the mean plane formed by the remaining ring atoms (N1/C6–C8 atoms). The mean-plane of the benzene ring C1–C6 makes a dihedral angle 23.43 (14)° with the mean-plane of the pyrazole ring (N2/N3/C7/C8/C9). The acetate group (O3/O4/C12/C13/C14) is essentially planar (rmsd 0.031 Å) and its mean-plane is oriented at 82.4 (2)° with respect to the pyrazole ring.
The crystal structure is stabilized by weak intermolecular C—H···O hydrogen bonds resulting in a three-dimensional network (Fig. 2 and Table 1).