


Supporting information
![]() | Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680800007X/hk2412sup1.cif |
![]() | Structure factor file (CIF format) https://doi.org/10.1107/S160053680800007X/hk2412Isup2.hkl |
CCDC reference: 677543
Key indicators
- Single-crystal X-ray study
- T = 296 K
- Mean
(C-C) = 0.004 Å
- R factor = 0.044
- wR factor = 0.124
- Data-to-parameter ratio = 19.6
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low ....... 0.98 PLAT062_ALERT_4_C Rescale T(min) & T(max) by ..................... 1.01 PLAT154_ALERT_1_C The su's on the Cell Angles are Equal (x 10000) 300 Deg. PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C10
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 4 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 1 ALERT type 2 Indicator that the structure model may be wrong or deficient 1 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
For the preparation of the title compound, the suspension of hexane-washed sodium hydride (50% in mineral oil) was prepared in dry dimethylformamide (3 ml). A solution of methyl N-methylsulfonylanthranilate (70 mg, 0.306 mmol) in dry dimethylformamide (5 ml) was added to the suspension (76 mg, 0.368 mmol), and stirred for 45 min at room temperature. Then, a solution of ethyl iodide (144 mg, 0.92 mmol) in ether (5 ml) was added to it. The resulting white suspension was stirred for 1.5 h and poured into hydrochloric acid (3 N, 50 ml) to produce a yellow suspension which was extracted with chloroform (4 × 25 ml). The combined extract was dried over calcium sulfate and evaporated under reduced pressure (11 torr) to get the title compound (yield; 58 mg, 73%, m.p. 330–331 K). Crystals suitable for X-ray analysis were obtained by slow evaporation of CHCl3.
H atoms were positioned geometrically, with C—H = 0.93, 0.97 and 0.96 Å for aromatic, methylene and methyl H, and constrained to ride on their parent atoms, with Uiso(H) = xUeq(C), where x = 1.5 for methyl H, and x = 1.2 for all other H atoms.
Data collection: APEX2 (Bruker, 2007); cell refinement: APEX2 (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 for Windows (Farrugia, 1997) and PLATON (Spek, 2003); software used to prepare material for publication: WinGX publication routines (Farrugia, 1999) and PLATON (Spek, 2003).
C11H15NO4S | Z = 2 |
Mr = 257.30 | F(000) = 272 |
Triclinic, P1 | Dx = 1.377 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 8.0161 (4) Å | Cell parameters from 3596 reflections |
b = 8.4386 (4) Å | θ = 2.7–24.8° |
c = 10.5329 (5) Å | µ = 0.26 mm−1 |
α = 85.244 (3)° | T = 296 K |
β = 78.721 (3)° | Prismatic, colourless |
γ = 62.650 (3)° | 0.25 × 0.18 × 0.12 mm |
V = 620.61 (5) Å3 |
Bruker KAPPA APEXII CCD diffractometer | 3012 independent reflections |
Radiation source: fine-focus sealed tube | 1817 reflections with I > 3σ(I) |
Graphite monochromator | Rint = 0.032 |
Detector resolution: 8.33 pixels mm-1 | θmax = 28.3°, θmin = 2.0° |
ω scans | h = −10→10 |
Absorption correction: multi-scan (SADABS; Bruker, 2005) | k = −11→11 |
Tmin = 0.935, Tmax = 0.958 | l = −14→14 |
11895 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)] = 0.043 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.123 | H-atom parameters constrained |
S = 1.00 | w = 1/[σ2(Fo2) + (0.0727P)2 + 0.1532P] where P = (Fo2 + 2Fc2)/3 |
3012 reflections | (Δ/σ)max < 0.001 |
154 parameters | Δρmax = 0.37 e Å−3 |
0 restraints | Δρmin = −0.36 e Å−3 |
C11H15NO4S | γ = 62.650 (3)° |
Mr = 257.30 | V = 620.61 (5) Å3 |
Triclinic, P1 | Z = 2 |
a = 8.0161 (4) Å | Mo Kα radiation |
b = 8.4386 (4) Å | µ = 0.26 mm−1 |
c = 10.5329 (5) Å | T = 296 K |
α = 85.244 (3)° | 0.25 × 0.18 × 0.12 mm |
β = 78.721 (3)° |
Bruker KAPPA APEXII CCD diffractometer | 3012 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2005) | 1817 reflections with I > 3σ(I) |
Tmin = 0.935, Tmax = 0.958 | Rint = 0.032 |
11895 measured reflections |
R[F2 > 2σ(F2)] = 0.043 | 0 restraints |
wR(F2) = 0.123 | H-atom parameters constrained |
S = 1.00 | Δρmax = 0.37 e Å−3 |
3012 reflections | Δρmin = −0.36 e Å−3 |
154 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 | ||
S1 | 0.14595 (10) | 0.13878 (8) | 0.07989 (5) | 0.0507 (2) | |
O1 | −0.0510 (3) | 0.1954 (3) | 0.08167 (19) | 0.0688 (6) | |
O2 | 0.2655 (3) | 0.1495 (3) | −0.03718 (16) | 0.0707 (6) | |
O3 | 0.2630 (3) | 0.0251 (3) | 0.40332 (17) | 0.0811 (7) | |
O4 | 0.0983 (3) | 0.1413 (3) | 0.59441 (16) | 0.0700 (6) | |
N1 | 0.1604 (3) | 0.2545 (3) | 0.18962 (17) | 0.0457 (5) | |
C1 | −0.0041 (3) | 0.3538 (3) | 0.2846 (2) | 0.0443 (6) | |
C2 | −0.0200 (3) | 0.3048 (3) | 0.4158 (2) | 0.0436 (6) | |
C3 | −0.1825 (4) | 0.4142 (4) | 0.5006 (3) | 0.0605 (7) | |
H3 | −0.195 | 0.3845 | 0.5878 | 0.073* | |
C4 | −0.3251 (4) | 0.5646 (4) | 0.4595 (4) | 0.0758 (9) | |
H4 | −0.4337 | 0.6344 | 0.5181 | 0.091* | |
C5 | −0.3076 (5) | 0.6121 (4) | 0.3320 (4) | 0.0801 (10) | |
H5 | −0.4039 | 0.7146 | 0.3039 | 0.096* | |
C6 | −0.1476 (4) | 0.5080 (4) | 0.2458 (3) | 0.0654 (8) | |
H6 | −0.1356 | 0.542 | 0.1596 | 0.078* | |
C7 | 0.3401 (4) | 0.2613 (4) | 0.1897 (2) | 0.0565 (7) | |
H7A | 0.4445 | 0.1594 | 0.1417 | 0.068* | |
H7B | 0.3614 | 0.2524 | 0.2781 | 0.068* | |
C8 | 0.3412 (5) | 0.4294 (5) | 0.1310 (3) | 0.0872 (11) | |
H8A | 0.4615 | 0.427 | 0.1332 | 0.131* | |
H8B | 0.2402 | 0.5307 | 0.1794 | 0.131* | |
H8C | 0.3228 | 0.4378 | 0.0429 | 0.131* | |
C9 | 0.2485 (4) | −0.0838 (3) | 0.1283 (2) | 0.0573 (7) | |
H9A | 0.3819 | −0.1245 | 0.1276 | 0.086* | |
H9B | 0.2333 | −0.1556 | 0.0697 | 0.086* | |
H9C | 0.1866 | −0.0938 | 0.2141 | 0.086* | |
C10 | 0.1286 (4) | 0.1421 (3) | 0.4659 (2) | 0.0457 (6) | |
C11 | 0.2403 (5) | −0.0050 (4) | 0.6546 (3) | 0.0754 (9) | |
H11A | 0.204 | 0.0075 | 0.747 | 0.113* | |
H11B | 0.3615 | −0.0042 | 0.6282 | 0.113* | |
H11C | 0.2499 | −0.1157 | 0.6285 | 0.113* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0718 (5) | 0.0469 (4) | 0.0342 (3) | −0.0235 (3) | −0.0201 (3) | 0.0011 (2) |
O1 | 0.0720 (13) | 0.0634 (12) | 0.0718 (12) | −0.0208 (10) | −0.0347 (10) | −0.0126 (9) |
O2 | 0.1094 (17) | 0.0694 (13) | 0.0324 (9) | −0.0411 (12) | −0.0106 (9) | 0.0037 (8) |
O3 | 0.0977 (16) | 0.0587 (12) | 0.0408 (10) | 0.0047 (11) | −0.0141 (10) | −0.0030 (9) |
O4 | 0.0661 (13) | 0.0920 (15) | 0.0355 (9) | −0.0220 (11) | −0.0101 (9) | 0.0021 (9) |
N1 | 0.0579 (13) | 0.0471 (11) | 0.0337 (9) | −0.0239 (10) | −0.0109 (9) | −0.0018 (8) |
C1 | 0.0527 (15) | 0.0365 (12) | 0.0475 (12) | −0.0200 (11) | −0.0169 (11) | −0.0023 (9) |
C2 | 0.0484 (14) | 0.0446 (13) | 0.0417 (12) | −0.0224 (12) | −0.0104 (11) | −0.0062 (10) |
C3 | 0.0547 (17) | 0.0681 (18) | 0.0569 (15) | −0.0256 (15) | −0.0035 (13) | −0.0186 (13) |
C4 | 0.0540 (19) | 0.065 (2) | 0.095 (2) | −0.0127 (16) | −0.0083 (17) | −0.0345 (17) |
C5 | 0.067 (2) | 0.0508 (17) | 0.106 (3) | −0.0015 (15) | −0.038 (2) | −0.0169 (17) |
C6 | 0.079 (2) | 0.0450 (15) | 0.0677 (17) | −0.0174 (15) | −0.0307 (16) | 0.0023 (12) |
C7 | 0.0632 (17) | 0.0686 (17) | 0.0439 (13) | −0.0347 (15) | −0.0087 (12) | −0.0046 (12) |
C8 | 0.122 (3) | 0.094 (3) | 0.075 (2) | −0.077 (2) | −0.013 (2) | 0.0089 (18) |
C9 | 0.0779 (19) | 0.0455 (14) | 0.0483 (14) | −0.0252 (14) | −0.0173 (13) | −0.0010 (11) |
C10 | 0.0556 (16) | 0.0491 (14) | 0.0348 (11) | −0.0255 (13) | −0.0077 (11) | −0.0016 (10) |
C11 | 0.082 (2) | 0.095 (2) | 0.0440 (14) | −0.0339 (18) | −0.0227 (15) | 0.0166 (14) |
S1—O1 | 1.421 (2) | C4—H4 | 0.93 |
S1—O2 | 1.4303 (19) | C5—C6 | 1.372 (4) |
S1—N1 | 1.6269 (18) | C5—H5 | 0.93 |
S1—C9 | 1.747 (2) | C6—H6 | 0.93 |
O3—C10 | 1.193 (3) | C7—C8 | 1.503 (4) |
O4—C10 | 1.328 (3) | C7—H7A | 0.97 |
O4—C11 | 1.443 (3) | C7—H7B | 0.97 |
N1—C1 | 1.431 (3) | C8—H8A | 0.96 |
N1—C7 | 1.468 (3) | C8—H8B | 0.96 |
C1—C6 | 1.380 (3) | C8—H8C | 0.96 |
C1—C2 | 1.408 (3) | C9—H9A | 0.96 |
C2—C3 | 1.387 (3) | C9—H9B | 0.96 |
C2—C10 | 1.485 (3) | C9—H9C | 0.96 |
C3—C4 | 1.369 (4) | C11—H11A | 0.96 |
C3—H3 | 0.93 | C11—H11B | 0.96 |
C4—C5 | 1.368 (5) | C11—H11C | 0.96 |
O1—S1—O2 | 119.88 (12) | N1—C7—C8 | 112.8 (2) |
O1—S1—N1 | 107.29 (11) | N1—C7—H7A | 109 |
O2—S1—N1 | 107.34 (11) | C8—C7—H7A | 109 |
O1—S1—C9 | 108.32 (13) | N1—C7—H7B | 109 |
O2—S1—C9 | 106.53 (13) | C8—C7—H7B | 109 |
N1—S1—C9 | 106.83 (11) | H7A—C7—H7B | 107.8 |
C10—O4—C11 | 116.5 (2) | C7—C8—H8A | 109.5 |
C1—N1—C7 | 119.82 (18) | C7—C8—H8B | 109.5 |
C1—N1—S1 | 119.87 (16) | H8A—C8—H8B | 109.5 |
C7—N1—S1 | 120.29 (16) | C7—C8—H8C | 109.5 |
C6—C1—C2 | 119.3 (2) | H8A—C8—H8C | 109.5 |
C6—C1—N1 | 118.0 (2) | H8B—C8—H8C | 109.5 |
C2—C1—N1 | 122.6 (2) | S1—C9—H9A | 109.5 |
C3—C2—C1 | 117.9 (2) | S1—C9—H9B | 109.5 |
C3—C2—C10 | 119.3 (2) | H9A—C9—H9B | 109.5 |
C1—C2—C10 | 122.8 (2) | S1—C9—H9C | 109.5 |
C4—C3—C2 | 121.8 (3) | H9A—C9—H9C | 109.5 |
C4—C3—H3 | 119.1 | H9B—C9—H9C | 109.5 |
C2—C3—H3 | 119.1 | O3—C10—O4 | 121.8 (2) |
C5—C4—C3 | 119.9 (3) | O3—C10—C2 | 126.8 (2) |
C5—C4—H4 | 120 | O4—C10—C2 | 111.4 (2) |
C3—C4—H4 | 120 | O4—C11—H11A | 109.5 |
C4—C5—C6 | 119.7 (3) | O4—C11—H11B | 109.5 |
C4—C5—H5 | 120.1 | H11A—C11—H11B | 109.5 |
C6—C5—H5 | 120.1 | O4—C11—H11C | 109.5 |
C5—C6—C1 | 121.3 (3) | H11A—C11—H11C | 109.5 |
C5—C6—H6 | 119.3 | H11B—C11—H11C | 109.5 |
C1—C6—H6 | 119.3 | ||
O1—S1—N1—C1 | 14.2 (2) | C10—C2—C3—C4 | −179.2 (2) |
O2—S1—N1—C1 | 144.26 (18) | C2—C3—C4—C5 | −1.2 (4) |
C9—S1—N1—C1 | −101.8 (2) | C3—C4—C5—C6 | 0.4 (5) |
O1—S1—N1—C7 | −164.23 (18) | C4—C5—C6—C1 | 1.0 (5) |
O2—S1—N1—C7 | −34.2 (2) | C2—C1—C6—C5 | −1.7 (4) |
C9—S1—N1—C7 | 79.8 (2) | N1—C1—C6—C5 | −178.6 (3) |
C7—N1—C1—C6 | 104.8 (3) | C1—N1—C7—C8 | −78.2 (3) |
S1—N1—C1—C6 | −73.6 (3) | S1—N1—C7—C8 | 100.3 (2) |
C7—N1—C1—C2 | −72.0 (3) | C11—O4—C10—O3 | 2.3 (4) |
S1—N1—C1—C2 | 109.6 (2) | C11—O4—C10—C2 | −176.2 (2) |
C6—C1—C2—C3 | 0.9 (3) | C3—C2—C10—O3 | 170.1 (3) |
N1—C1—C2—C3 | 177.6 (2) | C1—C2—C10—O3 | −9.6 (4) |
C6—C1—C2—C10 | −179.4 (2) | C3—C2—C10—O4 | −11.5 (3) |
N1—C1—C2—C10 | −2.7 (3) | C1—C2—C10—O4 | 168.9 (2) |
C1—C2—C3—C4 | 0.5 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
C9—H9B···O1i | 0.96 | 2.50 | 3.372 (5) | 151 |
C7—H7B···O3 | 0.97 | 2.57 | 3.044 (4) | 110 |
C9—H9C···O3 | 0.96 | 2.59 | 3.152 (4) | 117 |
Symmetry code: (i) −x, −y, −z. |
Experimental details
Crystal data | |
Chemical formula | C11H15NO4S |
Mr | 257.30 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 296 |
a, b, c (Å) | 8.0161 (4), 8.4386 (4), 10.5329 (5) |
α, β, γ (°) | 85.244 (3), 78.721 (3), 62.650 (3) |
V (Å3) | 620.61 (5) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.26 |
Crystal size (mm) | 0.25 × 0.18 × 0.12 |
Data collection | |
Diffractometer | Bruker KAPPA APEXII CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2005) |
Tmin, Tmax | 0.935, 0.958 |
No. of measured, independent and observed [I > 3σ(I)] reflections | 11895, 3012, 1817 |
Rint | 0.032 |
(sin θ/λ)max (Å−1) | 0.667 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.043, 0.123, 1.00 |
No. of reflections | 3012 |
No. of parameters | 154 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.37, −0.36 |
Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2003), WinGX publication routines (Farrugia, 1999) and PLATON (Spek, 2003).
S1—O1 | 1.421 (2) | O3—C10 | 1.193 (3) |
S1—O2 | 1.4303 (19) | O4—C10 | 1.328 (3) |
S1—N1 | 1.6269 (18) | O4—C11 | 1.443 (3) |
S1—C9 | 1.747 (2) | ||
O1—S1—O2 | 119.88 (12) | N1—S1—C9 | 106.83 (11) |
O1—S1—N1 | 107.29 (11) | C10—O4—C11 | 116.5 (2) |
O2—S1—N1 | 107.34 (11) | O3—C10—O4 | 121.8 (2) |
O1—S1—C9 | 108.32 (13) | O3—C10—C2 | 126.8 (2) |
O2—S1—C9 | 106.53 (13) | O4—C10—C2 | 111.4 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
C9—H9B···O1i | 0.96 | 2.50 | 3.372 (5) | 151 |
C7—H7B···O3 | 0.97 | 2.57 | 3.044 (4) | 110 |
C9—H9C···O3 | 0.96 | 2.59 | 3.152 (4) | 117 |
Symmetry code: (i) −x, −y, −z. |
Alkyl anthranilates are valuable starting materials for the preparation of pesticides, dyes and drugs (Reissenweber & Mangold, 1982). They find organoleptic uses in augmenting the aroma or taste of perfume compositions, colognes, perfumed articles, foodstuffs, medicinal products and in enhancing the effects of deodorancy (Mookherjee et al., 1989). Particularly, the N-substituted thioesters of anthranilic acid have been found potent inhibitors of the serine proteases human leukocyte (HL) elastase, porcine pancreatic elastase, cathepsin G, and bovine chymotrypsin Aα (Tadashi et al., 1982). In continuation of our research program to synthesize new biologically important 1,2-benzothiazine 1,1-dioxide molecules (Siddiqui et al., 2006; Siddiqui et al., 2007a,b), we embarked on the syntheses of 2,1-benzothiazine 2,2-dioxide, as well. Contrary to the N-methyl substituent (Lombardino, 1972), the N-ethyl derivative is being reported for the first time.
The title compound, (I), is an important precursor for the synthesis of 2,1-benzothiazine 2,2-dioxide molecule. The structure determination of (I) is undertaken in order to understand the conformational geometry around the sulfur and nitrogen atoms, due to the addition of ethyl group.
In the molecule of (I), (Fig. 1) S1 atom adopts a distorted tetrahedral coordination geometry with two O, one N and one C atoms of methylsulfonyl amino group (Table 1). The sulfur bonds are shortened, while the bond angles aroud it are different with respect to the corresponding values reported in methyl anthranilate N-methanesulfonamide, (II), (Hanson & Hitchcook, 2004).
In (I), the addition of ethyl group at N1, instead of H-atom in (II), has changed the orientation of CH3 group and O4 atom as compared with (II). On the other hand, the O3—C10 [1.193 (3) Å] and O4—C10 [1.328 (3) Å] bonds in (I), are reported as 1.2202 (16) Å and 1.3324 (16) Å, respectively, in (II). The methyl carboxylate group (O3/O4/C10/C11) is oriented at a dihedral angle of 11.8 (2)° with respect to the phenyl ring (C1—C6).
In the crystal structure, intermolecular C—H···O hydrogen bonds (Table 2) link the molecules into centrosymmetric dimers (Fig. 2), in which they may be effective in the stabilization of the structure.