The crystal structure of the title compound, C
12H
13NO
3S, is stabilized by intermolecular N—H
O hydrogen bonds, which are formed between the NH groups and the sulfoxide O atoms.
Supporting information
CCDC reference: 282647
Key indicators
- Single-crystal X-ray study
- T = 296 K
- Mean (C-C) = 0.004 Å
- R factor = 0.033
- wR factor = 0.082
- Data-to-parameter ratio = 15.1
checkCIF/PLATON results
No syntax errors found
Alert level C
PLAT220_ALERT_2_C Large Non-Solvent C Ueq(max)/Ueq(min) ... 2.79 Ratio
PLAT222_ALERT_3_C Large Non-Solvent H Ueq(max)/Ueq(min) ... 3.14 Ratio
PLAT230_ALERT_2_C Hirshfeld Test Diff for S1 - C6 .. 5.15 su
Alert level G
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
correct. If it is not, please give the correct count in the
_publ_section_exptl_refinement section of the submitted CIF.
From the CIF: _diffrn_reflns_theta_max 27.15
From the CIF: _reflns_number_total 2369
Count of symmetry unique reflns 1392
Completeness (_total/calc) 170.19%
TEST3: Check Friedels for noncentro structure
Estimate of Friedel pairs measured 977
Fraction of Friedel pairs measured 0.702
Are heavy atom types Z>Si present yes
0 ALERT level A = In general: serious problem
0 ALERT level B = Potentially serious problem
3 ALERT level C = Check and explain
1 ALERT level G = General alerts; check
0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
2 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
Data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA; data reduction: X-RED32 (Stoe & Cie, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).
Ethyl 3-methyl-1-oxo-4
H-1,4-benzothiazine-2-carboxylate
top
Crystal data top
C12H13NO3S | F(000) = 2112 |
Mr = 251.30 | Dx = 1.394 Mg m−3 |
Orthorhombic, Fdd2 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: F 2 -2d | Cell parameters from 9568 reflections |
a = 12.9935 (13) Å | θ = 2.5–27.3° |
b = 33.042 (4) Å | µ = 0.27 mm−1 |
c = 11.1555 (13) Å | T = 296 K |
V = 4789.4 (9) Å3 | Prism, pale yellow |
Z = 16 | 0.58 × 0.32 × 0.10 mm |
Data collection top
Stoe IPDS-II diffractometer | 2369 independent reflections |
Radiation source: sealed X-ray tube, 12 x 0.4 mm long-fine focus | 2037 reflections with I > 2σ(I) |
Plane graphite monochromator | Rint = 0.034 |
Detector resolution: 6.67 pixels mm-1 | θmax = 27.2°, θmin = 2.5° |
ω scans | h = −16→16 |
Absorption correction: integration (X-RED32; Stoe & Cie, 2002) | k = −41→40 |
Tmin = 0.861, Tmax = 0.974 | l = −12→14 |
6798 measured reflections | |
Refinement top
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.033 | w = 1/[σ2(Fo2) + (0.0541P)2] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.082 | (Δ/σ)max < 0.001 |
S = 1.00 | Δρmax = 0.33 e Å−3 |
2369 reflections | Δρmin = −0.18 e Å−3 |
157 parameters | Extinction correction: SHELXL97, FC*=KFC[1+0.001XFC2Λ3/SIN(2Θ)]-1/4 |
1 restraint | Extinction coefficient: 0.0009 (2) |
Primary atom site location: structure-invariant direct methods | Absolute structure: Flack (1983), 977 Friedel pairs |
Secondary atom site location: difference Fourier map | Absolute structure parameter: 0.001 (3) |
Special details top
Geometry. Bond distances, angles etc. have been calculated using the rounded
fractional coordinates. All su's are estimated from the variances of the
(full) variance-covariance matrix. The cell e.s.d.'s are taken into account in
the estimation of distances, angles and torsion angles |
Refinement. Refinement on F2 for ALL reflections except those flagged by the user
for potential systematic errors. Weighted R-factors wR and all
goodnesses of fit S are based on F2, conventional
R-factors R are based on F, with F set to zero for
negative F2. The observed criterion of F2 > σ(F2)
is used only for calculating -R-factor-obs 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) top | x | y | z | Uiso*/Ueq | |
S1 | 0.11438 (4) | 0.22389 (1) | 0.41762 (4) | 0.0380 (1) | |
O1 | 0.00760 (14) | 0.20995 (5) | 0.38434 (15) | 0.0510 (6) | |
O2 | 0.12503 (17) | 0.33960 (5) | 0.36163 (19) | 0.0633 (7) | |
O3 | 0.12934 (14) | 0.28300 (5) | 0.25140 (15) | 0.0500 (6) | |
N1 | 0.07603 (14) | 0.26397 (5) | 0.66416 (17) | 0.0408 (5) | |
C1 | 0.11329 (14) | 0.22473 (6) | 0.66626 (19) | 0.0375 (6) | |
C2 | 0.12719 (19) | 0.20536 (9) | 0.7769 (2) | 0.0504 (8) | |
C3 | 0.1628 (2) | 0.16653 (9) | 0.7801 (2) | 0.0573 (9) | |
C4 | 0.1871 (2) | 0.14584 (8) | 0.6762 (3) | 0.0564 (8) | |
C5 | 0.17560 (19) | 0.16488 (7) | 0.5674 (2) | 0.0463 (7) | |
C6 | 0.13752 (15) | 0.20439 (7) | 0.56190 (19) | 0.0369 (6) | |
C7 | 0.10662 (16) | 0.27514 (7) | 0.45611 (19) | 0.0378 (6) | |
C8 | 0.07635 (17) | 0.28856 (6) | 0.5677 (2) | 0.0381 (6) | |
C9 | 0.0408 (2) | 0.33058 (7) | 0.5941 (2) | 0.0523 (8) | |
C10 | 0.12073 (17) | 0.30315 (7) | 0.3555 (2) | 0.0431 (7) | |
C11 | 0.1445 (2) | 0.30665 (9) | 0.1440 (2) | 0.0652 (10) | |
C12 | 0.2532 (3) | 0.31506 (14) | 0.1235 (4) | 0.1030 (19) | |
H1 | 0.05060 | 0.27340 | 0.72960 | 0.0490* | |
H2 | 0.11220 | 0.21890 | 0.84790 | 0.0600* | |
H3 | 0.17090 | 0.15370 | 0.85380 | 0.0690* | |
H4 | 0.21100 | 0.11930 | 0.67980 | 0.0680* | |
H5 | 0.19330 | 0.15140 | 0.49720 | 0.0560* | |
H9A | 0.00680 | 0.33110 | 0.67050 | 0.0780* | |
H9B | −0.00630 | 0.33920 | 0.53290 | 0.0780* | |
H9C | 0.09900 | 0.34850 | 0.59580 | 0.0780* | |
H11A | 0.10730 | 0.33200 | 0.15120 | 0.0780* | |
H11B | 0.11680 | 0.29210 | 0.07580 | 0.0780* | |
H12A | 0.28240 | 0.32720 | 0.19380 | 0.1540* | |
H12B | 0.26030 | 0.33320 | 0.05680 | 0.1540* | |
H12C | 0.28870 | 0.29020 | 0.10620 | 0.1540* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
S1 | 0.0528 (3) | 0.0331 (2) | 0.0282 (2) | 0.0001 (2) | 0.0013 (2) | −0.0010 (2) |
O1 | 0.0700 (11) | 0.0429 (9) | 0.0402 (9) | −0.0140 (7) | −0.0187 (7) | 0.0066 (7) |
O2 | 0.0918 (15) | 0.0366 (10) | 0.0615 (12) | −0.0072 (9) | 0.0094 (9) | 0.0094 (9) |
O3 | 0.0675 (10) | 0.0462 (10) | 0.0362 (9) | −0.0024 (7) | 0.0038 (7) | 0.0097 (7) |
N1 | 0.0538 (9) | 0.0370 (9) | 0.0315 (8) | 0.0030 (7) | 0.0081 (8) | −0.0039 (8) |
C1 | 0.0421 (10) | 0.0365 (11) | 0.0339 (11) | 0.0001 (7) | 0.0008 (10) | −0.0009 (10) |
C2 | 0.0648 (14) | 0.0550 (15) | 0.0314 (12) | 0.0034 (11) | −0.0016 (10) | 0.0009 (11) |
C3 | 0.0738 (17) | 0.0574 (17) | 0.0407 (13) | 0.0055 (12) | −0.0080 (12) | 0.0126 (12) |
C4 | 0.0675 (14) | 0.0436 (13) | 0.0580 (15) | 0.0126 (11) | −0.0034 (13) | 0.0076 (12) |
C5 | 0.0553 (13) | 0.0397 (12) | 0.0438 (12) | 0.0084 (10) | 0.0000 (10) | −0.0056 (10) |
C6 | 0.0415 (11) | 0.0333 (11) | 0.0359 (11) | −0.0010 (8) | 0.0002 (8) | −0.0006 (9) |
C7 | 0.0451 (11) | 0.0310 (10) | 0.0373 (11) | −0.0021 (8) | 0.0005 (8) | 0.0019 (8) |
C8 | 0.0430 (10) | 0.0320 (11) | 0.0392 (11) | −0.0030 (8) | 0.0027 (8) | −0.0018 (9) |
C9 | 0.0634 (14) | 0.0372 (13) | 0.0564 (15) | 0.0049 (11) | 0.0100 (11) | −0.0022 (11) |
C10 | 0.0470 (12) | 0.0392 (13) | 0.0431 (12) | −0.0015 (9) | 0.0012 (9) | 0.0046 (10) |
C11 | 0.0831 (19) | 0.0703 (18) | 0.0422 (17) | 0.0003 (15) | 0.0064 (12) | 0.0226 (13) |
C12 | 0.104 (3) | 0.124 (4) | 0.081 (3) | −0.021 (2) | 0.016 (2) | 0.037 (3) |
Geometric parameters (Å, º) top
S1—O1 | 1.5083 (19) | C7—C10 | 1.466 (3) |
S1—C6 | 1.760 (2) | C8—C9 | 1.493 (3) |
S1—C7 | 1.750 (2) | C11—C12 | 1.458 (5) |
O2—C10 | 1.208 (3) | C2—H2 | 0.9300 |
O3—C10 | 1.343 (3) | C3—H3 | 0.9300 |
O3—C11 | 1.444 (3) | C4—H4 | 0.9300 |
N1—C1 | 1.384 (3) | C5—H5 | 0.9300 |
N1—C8 | 1.348 (3) | C9—H9A | 0.9600 |
N1—H1 | 0.8600 | C9—H9B | 0.9600 |
C1—C6 | 1.381 (3) | C9—H9C | 0.9600 |
C1—C2 | 1.402 (3) | C11—H11A | 0.9700 |
C2—C3 | 1.364 (4) | C11—H11B | 0.9700 |
C3—C4 | 1.382 (4) | C12—H12A | 0.9600 |
C4—C5 | 1.375 (4) | C12—H12B | 0.9600 |
C5—C6 | 1.398 (3) | C12—H12C | 0.9600 |
C7—C8 | 1.379 (3) | | |
| | | |
S1···O3 | 2.7002 (18) | C11···C1ii | 3.515 (3) |
S1···N1 | 3.0930 (19) | C12···O2 | 3.239 (5) |
S1···C7i | 3.651 (2) | C4···H9Ci | 2.9300 |
S1···C10i | 3.623 (2) | C5···H9Ci | 2.9800 |
S1···H1ii | 3.0000 | C7···H2ii | 3.1000 |
O1···N1ii | 2.821 (3) | C9···H5vii | 2.9000 |
O2···C12 | 3.239 (5) | C10···H9C | 3.0800 |
O2···C9iii | 3.411 (3) | C10···H12A | 2.8800 |
O2···C9 | 2.831 (3) | C10···H9B | 2.8400 |
O3···C1ii | 3.303 (3) | H1···H2 | 2.3700 |
O3···C2ii | 3.367 (3) | H1···H9A | 2.1000 |
O3···N1ii | 3.237 (3) | H1···S1iv | 3.0000 |
O3···S1 | 2.7002 (18) | H1···O1iv | 1.9600 |
O1···H9Aii | 2.7500 | H2···H1 | 2.3700 |
O1···H11Biv | 2.6800 | H2···O1iv | 2.8500 |
O1···H1ii | 1.9600 | H2···C7iv | 3.1000 |
O1···H2ii | 2.8500 | H3···H11Aviii | 2.4500 |
O1···H4v | 2.7400 | H3···H12Bix | 2.4700 |
O2···H5i | 2.8200 | H4···O1x | 2.7400 |
O2···H12A | 2.8000 | H5···C9xi | 2.9000 |
O2···H9B | 2.5600 | H5···H9Axi | 2.5600 |
O2···H9C | 2.6500 | H5···H9Cxi | 2.4900 |
O2···H11A | 2.3700 | H5···O2i | 2.8200 |
N1···S1 | 3.0930 (19) | H9A···H1 | 2.1000 |
N1···O1iv | 2.821 (3) | H9A···H5vii | 2.5600 |
N1···O3iv | 3.237 (3) | H9A···O1iv | 2.7500 |
C1···O3iv | 3.303 (3) | H9B···O2 | 2.5600 |
C1···C11iv | 3.515 (3) | H9B···C10 | 2.8400 |
C2···O3iv | 3.367 (3) | H9C···O2 | 2.6500 |
C2···C10iv | 3.350 (3) | H9C···C10 | 3.0800 |
C5···C8i | 3.571 (3) | H9C···H5vii | 2.4900 |
C6···C7i | 3.592 (3) | H9C···C4i | 2.9300 |
C7···S1i | 3.651 (2) | H9C···C5i | 2.9800 |
C7···C6i | 3.592 (3) | H11A···O2 | 2.3700 |
C8···C5i | 3.571 (3) | H11A···H3xii | 2.4500 |
C9···O2vi | 3.411 (3) | H11B···O1ii | 2.6800 |
C9···O2 | 2.831 (3) | H12A···O2 | 2.8000 |
C10···S1i | 3.623 (2) | H12A···C10 | 2.8800 |
C10···C2ii | 3.350 (3) | H12B···H3xiii | 2.4700 |
| | | |
O1—S1—C6 | 105.70 (10) | O3—C11—C12 | 111.4 (3) |
O1—S1—C7 | 107.63 (10) | C1—C2—H2 | 120.00 |
C6—S1—C7 | 98.03 (10) | C3—C2—H2 | 120.00 |
C10—O3—C11 | 117.42 (19) | C2—C3—H3 | 119.00 |
C1—N1—C8 | 125.23 (19) | C4—C3—H3 | 119.00 |
C8—N1—H1 | 117.00 | C3—C4—H4 | 120.00 |
C1—N1—H1 | 117.00 | C5—C4—H4 | 120.00 |
N1—C1—C6 | 121.43 (19) | C4—C5—H5 | 120.00 |
N1—C1—C2 | 119.2 (2) | C6—C5—H5 | 120.00 |
C2—C1—C6 | 119.4 (2) | C8—C9—H9A | 110.00 |
C1—C2—C3 | 119.7 (2) | C8—C9—H9B | 109.00 |
C2—C3—C4 | 121.4 (2) | C8—C9—H9C | 109.00 |
C3—C4—C5 | 119.3 (2) | H9A—C9—H9B | 109.00 |
C4—C5—C6 | 120.3 (2) | H9A—C9—H9C | 109.00 |
S1—C6—C5 | 116.28 (16) | H9B—C9—H9C | 109.00 |
C1—C6—C5 | 119.9 (2) | O3—C11—H11A | 109.00 |
S1—C6—C1 | 123.65 (17) | O3—C11—H11B | 109.00 |
C8—C7—C10 | 121.6 (2) | C12—C11—H11A | 109.00 |
S1—C7—C8 | 123.31 (17) | C12—C11—H11B | 109.00 |
S1—C7—C10 | 114.57 (16) | H11A—C11—H11B | 108.00 |
C7—C8—C9 | 124.4 (2) | C11—C12—H12A | 110.00 |
N1—C8—C7 | 121.85 (19) | C11—C12—H12B | 109.00 |
N1—C8—C9 | 113.71 (19) | C11—C12—H12C | 109.00 |
O2—C10—O3 | 122.6 (2) | H12A—C12—H12B | 110.00 |
O2—C10—C7 | 126.3 (2) | H12A—C12—H12C | 109.00 |
O3—C10—C7 | 111.06 (19) | H12B—C12—H12C | 109.00 |
| | | |
O1—S1—C6—C5 | 85.45 (18) | N1—C1—C2—C3 | 179.3 (2) |
C7—S1—C6—C5 | −163.61 (18) | C2—C1—C6—S1 | 174.97 (17) |
O1—S1—C7—C8 | 82.2 (2) | N1—C1—C6—S1 | −5.4 (3) |
C6—S1—C7—C8 | −27.2 (2) | C6—C1—C2—C3 | −1.1 (3) |
O1—S1—C7—C10 | −89.56 (17) | C1—C2—C3—C4 | 0.9 (4) |
C6—S1—C7—C10 | 161.07 (16) | C2—C3—C4—C5 | 0.3 (4) |
O1—S1—C6—C1 | −89.75 (19) | C3—C4—C5—C6 | −1.5 (4) |
C7—S1—C6—C1 | 21.19 (19) | C4—C5—C6—S1 | −174.06 (19) |
C11—O3—C10—O2 | 0.1 (3) | C4—C5—C6—C1 | 1.3 (3) |
C11—O3—C10—C7 | −179.51 (19) | S1—C7—C10—O2 | −175.0 (2) |
C10—O3—C11—C12 | 86.8 (3) | C10—C7—C8—N1 | −171.3 (2) |
C1—N1—C8—C9 | −174.35 (19) | C10—C7—C8—C9 | 9.1 (3) |
C8—N1—C1—C2 | 167.4 (2) | S1—C7—C8—N1 | 17.5 (3) |
C1—N1—C8—C7 | 6.0 (3) | S1—C7—C8—C9 | −162.10 (18) |
C8—N1—C1—C6 | −12.3 (3) | C8—C7—C10—O2 | 13.1 (4) |
C2—C1—C6—C5 | −0.1 (3) | C8—C7—C10—O3 | −167.3 (2) |
N1—C1—C6—C5 | 179.59 (19) | S1—C7—C10—O3 | 4.6 (2) |
Symmetry codes: (i) −x+1/2, −y+1/2, z; (ii) −x, −y+1/2, z−1/2; (iii) x+1/4, −y+3/4, z−1/4; (iv) −x, −y+1/2, z+1/2; (v) x−1/4, −y+1/4, z−1/4; (vi) x−1/4, −y+3/4, z+1/4; (vii) −x+1/4, y+1/4, z+1/4; (viii) −x+1/4, y−1/4, z+3/4; (ix) −x+1/2, −y+1/2, z+1; (x) x+1/4, −y+1/4, z+1/4; (xi) −x+1/4, y−1/4, z−1/4; (xii) −x+1/4, y+1/4, z−3/4; (xiii) −x+1/2, −y+1/2, z−1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O1iv | 0.86 | 1.96 | 2.821 (3) | 175 |
Symmetry code: (iv) −x, −y+1/2, z+1/2. |