organic compounds
Methyl 2-(2,3,5-trimethyl-1,1-dioxo-2H-1λ6,2,6-thiadiazin-4-yl)benzoate
aChemistry Department, JJT University, Rajasthan, India, bSchool of Chemistry & Physics, University of KwaZulu-Natal, Durban 4000, South Africa, cDepartment of Chemistry, Government Science College, Gandhinagar, Gujarat, India, and dSchool of Pharmacology, University of KwaZulu Natal, Westville Campus, Private Bag X54001, South Africa
*Correspondence e-mail: maguireg@ukzn.ac.za
There are two molecules, A and B, in the of the title compound, C14H16N2O4S, which is the first example reported in this family of compounds in which the Nsp3 atom of the thiadiazine ring is methylated. The thiadiazine rings adopt shallow envelope conformations, with the S atoms displaced by 0.319 (12) and 0.182 (12) Å from the mean planes of the other ring atoms in molecules A and B, respectively. The dihedral angles between the thiadiazine mean planes (excluding S) and the attached benzene rings are 86.8 (3) and 86.7 (3)° for molecules A and B, respectively.
Related literature
For synthetic background, see: Wright (1964). For a related structure, see: Bhatt et al. (2012). For puckering parameters, see: Cremer & Pople (1975).
Experimental
Crystal data
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Data collection: COLLECT (Nonius, 2000); cell DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: SHELXL97.
Supporting information
10.1107/S1600536812046375/hb6962sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536812046375/hb6962Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536812046375/hb6962Isup3.cml
2-(3, 5-dimethyl-1, 1-dioxo-2H-1, 2, 6-thiadiazin-4-yl) benzoic acid (4.75 g,17 mmole) was dissolved in acetone (125 ml), to this K2CO3 (11.75 g, 85 mmole) was added slowly and then stirred for 10–15 min. Methyl iodide (7.23 g, 51 mmole) was added and reaction mixture was refluxed for 3 hrs. The reaction progress was monitored by TLC using ethyl acetate/hexane (8:2,Rf = 0.8). Excess solvent was completely evaporated under vacuum. The residue was treated with conc.HCl to get 2-(2,3,5-trimethyl-1,1-dioxido-2H-1,2,6-thiadiazin-4-yl)benzoic acid as a white solid (4.3 g Yield: 81.9%).
2-(2,3,5-trimethyl-1,1-dioxido-2H-1,2,6-thiadiazin-4-yl)benzoic acid (2.94 g, 10 mmole) was dissolved in methanol (25 ml), to this solution thionyl chloride (5.95 g, 50 mmole) was added slowly and the reaction mixture was refluxed for 3 hrs. The reaction progress was monitored by TLC using ethyl acetate/hexane (8:2,Rf = 0.8). Excess solvent was completely evaporated under vacuum. The residue was purified by silica gel column using methanol/ethyl acetate (1:9) as the
to afford the methyl ester as a colourless solid. (1.34 g,Yield: 55%).M.p.= 260 KRecrystallization using dioxane/water at room temperature afforded yellow blocks.
All hydrogen atoms were placed in idealized positions and refined with geometrical constraints. Flack x parameter is -0.0586 with e.s.d. 0.0543.
Data collection: COLLECT (Nonius, 2000); cell
DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).Fig. 1. The molecular structure of the title compound with H atoms omitted for clarity. Displacement ellipsoids are drawn at 40% probability. |
C14H16N2O4S | Dx = 1.439 Mg m−3 |
Mr = 308.35 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, Pna21 | Cell parameters from 33574 reflections |
a = 13.5954 (3) Å | θ = 2.6–27.5° |
b = 8.0683 (2) Å | µ = 0.25 mm−1 |
c = 25.9554 (7) Å | T = 173 K |
V = 2847.09 (12) Å3 | Block, yellow |
Z = 8 | 0.28 × 0.22 × 0.21 mm |
F(000) = 1296 |
Nonius KappaCCD diffractometer | 6094 independent reflections |
Radiation source: fine-focus sealed tube | 4522 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.057 |
1.2° ϕ scans and ω scans | θmax = 27.5°, θmin = 2.6° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −17→17 |
Tmin = 0.935, Tmax = 0.950 | k = −10→10 |
33574 measured reflections | l = −33→30 |
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.037 | w = 1/[σ2(Fo2) + (0.0445P)2] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.083 | (Δ/σ)max < 0.001 |
S = 0.99 | Δρmax = 0.21 e Å−3 |
6094 reflections | Δρmin = −0.25 e Å−3 |
388 parameters | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
1 restraint | Extinction coefficient: 0.0022 (4) |
Primary atom site location: structure-invariant direct methods | Absolute structure: Flack (1983), 2751 Friedel pairs |
Secondary atom site location: difference Fourier map | Absolute structure parameter: −0.06 (5) |
C14H16N2O4S | V = 2847.09 (12) Å3 |
Mr = 308.35 | Z = 8 |
Orthorhombic, Pna21 | Mo Kα radiation |
a = 13.5954 (3) Å | µ = 0.25 mm−1 |
b = 8.0683 (2) Å | T = 173 K |
c = 25.9554 (7) Å | 0.28 × 0.22 × 0.21 mm |
Nonius KappaCCD diffractometer | 6094 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 4522 reflections with I > 2σ(I) |
Tmin = 0.935, Tmax = 0.950 | Rint = 0.057 |
33574 measured reflections |
R[F2 > 2σ(F2)] = 0.037 | H-atom parameters constrained |
wR(F2) = 0.083 | Δρmax = 0.21 e Å−3 |
S = 0.99 | Δρmin = −0.25 e Å−3 |
6094 reflections | Absolute structure: Flack (1983), 2751 Friedel pairs |
388 parameters | Absolute structure parameter: −0.06 (5) |
1 restraint |
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 | ||
S1A | 0.16819 (4) | 0.24471 (7) | 0.03146 (3) | 0.02850 (14) | |
O1A | 0.17683 (12) | 0.3922 (2) | 0.06114 (8) | 0.0473 (5) | |
O2A | 0.19297 (13) | 0.2610 (2) | −0.02157 (7) | 0.0484 (5) | |
O3A | 0.01809 (15) | 0.1560 (2) | 0.18508 (7) | 0.0479 (5) | |
O4A | 0.01511 (13) | 0.01517 (19) | 0.25899 (7) | 0.0390 (4) | |
N1A | 0.22849 (14) | 0.0982 (2) | 0.05644 (9) | 0.0407 (6) | |
N2A | 0.05030 (13) | 0.1839 (2) | 0.03452 (8) | 0.0281 (4) | |
C1A | 0.26014 (19) | −0.1285 (4) | 0.11282 (13) | 0.0533 (9) | |
H1A1 | 0.3238 | −0.1211 | 0.0953 | 0.080* | |
H1A2 | 0.2355 | −0.2424 | 0.1107 | 0.080* | |
H1A3 | 0.2680 | −0.0971 | 0.1491 | 0.080* | |
C2A | 0.18851 (17) | −0.0136 (3) | 0.08748 (10) | 0.0324 (6) | |
C3A | 0.08626 (17) | −0.0289 (2) | 0.09642 (9) | 0.0242 (5) | |
C4A | 0.02022 (16) | 0.0661 (3) | 0.06916 (9) | 0.0252 (5) | |
C5A | −0.08899 (15) | 0.0468 (3) | 0.07394 (11) | 0.0315 (6) | |
H5A1 | −0.1181 | 0.1524 | 0.0847 | 0.047* | |
H5A2 | −0.1038 | −0.0384 | 0.0997 | 0.047* | |
H5A3 | −0.1165 | 0.0138 | 0.0406 | 0.047* | |
C6A | −0.01996 (19) | 0.2803 (3) | 0.00249 (11) | 0.0439 (7) | |
H6A1 | −0.0556 | 0.2049 | −0.0205 | 0.066* | |
H6A2 | 0.0163 | 0.3619 | −0.0181 | 0.066* | |
H6A3 | −0.0669 | 0.3377 | 0.0249 | 0.066* | |
C7A | 0.04993 (16) | −0.1651 (3) | 0.13101 (10) | 0.0254 (5) | |
C8A | 0.02189 (16) | −0.1410 (3) | 0.18317 (9) | 0.0248 (5) | |
C9A | −0.00644 (17) | −0.2776 (3) | 0.21258 (11) | 0.0334 (6) | |
H9A | −0.0260 | −0.2618 | 0.2474 | 0.040* | |
C10A | −0.00654 (18) | −0.4363 (3) | 0.19185 (10) | 0.0359 (6) | |
H10A | −0.0251 | −0.5284 | 0.2125 | 0.043* | |
C11A | 0.02038 (17) | −0.4595 (3) | 0.14124 (11) | 0.0343 (6) | |
H11A | 0.0201 | −0.5677 | 0.1268 | 0.041* | |
C12A | 0.04773 (17) | −0.3253 (3) | 0.11149 (10) | 0.0299 (6) | |
H12A | 0.0656 | −0.3431 | 0.0765 | 0.036* | |
C13A | 0.01886 (17) | 0.0251 (3) | 0.20735 (10) | 0.0303 (6) | |
C14A | 0.0134 (2) | 0.1689 (3) | 0.28670 (11) | 0.0429 (7) | |
H14A | 0.0672 | 0.2399 | 0.2747 | 0.064* | |
H14B | 0.0214 | 0.1471 | 0.3236 | 0.064* | |
H14C | −0.0496 | 0.2248 | 0.2808 | 0.064* | |
S1B | 0.10386 (4) | 0.26833 (7) | 0.45180 (2) | 0.02889 (15) | |
O1B | 0.08708 (12) | 0.3200 (2) | 0.50324 (7) | 0.0447 (5) | |
O2B | 0.08897 (11) | 0.09637 (19) | 0.44206 (8) | 0.0484 (5) | |
O3B | 0.24965 (14) | 0.35986 (19) | 0.29068 (7) | 0.0485 (5) | |
O4B | 0.24683 (13) | 0.50555 (18) | 0.21771 (7) | 0.0395 (5) | |
N1B | 0.04139 (13) | 0.3758 (2) | 0.41302 (9) | 0.0339 (5) | |
N2B | 0.22197 (13) | 0.3092 (2) | 0.43775 (8) | 0.0281 (5) | |
C1B | 0.00445 (19) | 0.5920 (4) | 0.35389 (13) | 0.0504 (8) | |
H1B1 | 0.0175 | 0.5786 | 0.3170 | 0.076* | |
H1B2 | 0.0086 | 0.7096 | 0.3631 | 0.076* | |
H1B3 | −0.0616 | 0.5504 | 0.3618 | 0.076* | |
C2B | 0.07937 (18) | 0.4957 (3) | 0.38431 (9) | 0.0285 (5) | |
C3B | 0.18034 (17) | 0.5317 (3) | 0.38014 (9) | 0.0243 (5) | |
C4B | 0.24909 (16) | 0.4372 (3) | 0.40624 (9) | 0.0242 (5) | |
C5B | 0.35705 (16) | 0.4635 (3) | 0.40010 (11) | 0.0332 (6) | |
H5B1 | 0.3863 | 0.4888 | 0.4337 | 0.050* | |
H5B2 | 0.3686 | 0.5562 | 0.3765 | 0.050* | |
H5B3 | 0.3872 | 0.3628 | 0.3861 | 0.050* | |
C6B | 0.29451 (18) | 0.2085 (3) | 0.46649 (11) | 0.0398 (7) | |
H6B1 | 0.3402 | 0.1565 | 0.4422 | 0.060* | |
H6B2 | 0.2601 | 0.1224 | 0.4861 | 0.060* | |
H6B3 | 0.3312 | 0.2799 | 0.4902 | 0.060* | |
C7B | 0.21176 (16) | 0.6741 (2) | 0.34682 (10) | 0.0250 (5) | |
C8B | 0.23889 (15) | 0.6576 (3) | 0.29426 (10) | 0.0259 (5) | |
C9B | 0.26085 (17) | 0.7992 (3) | 0.26573 (10) | 0.0318 (6) | |
H9B | 0.2788 | 0.7882 | 0.2305 | 0.038* | |
C10B | 0.25717 (18) | 0.9542 (3) | 0.28739 (11) | 0.0367 (6) | |
H10B | 0.2726 | 1.0490 | 0.2672 | 0.044* | |
C11B | 0.23110 (18) | 0.9722 (3) | 0.33840 (10) | 0.0348 (6) | |
H11B | 0.2286 | 1.0794 | 0.3535 | 0.042* | |
C12B | 0.20849 (18) | 0.8329 (3) | 0.36763 (10) | 0.0313 (6) | |
H12B | 0.1903 | 0.8465 | 0.4027 | 0.038* | |
C13B | 0.24545 (16) | 0.4921 (3) | 0.26875 (10) | 0.0283 (6) | |
C14B | 0.2508 (2) | 0.3515 (3) | 0.18876 (10) | 0.0433 (7) | |
H14D | 0.3151 | 0.2989 | 0.1939 | 0.065* | |
H14E | 0.2412 | 0.3748 | 0.1520 | 0.065* | |
H14F | 0.1989 | 0.2768 | 0.2008 | 0.065* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1A | 0.0315 (3) | 0.0281 (3) | 0.0259 (3) | −0.0024 (3) | 0.0061 (3) | 0.0015 (3) |
O1A | 0.0388 (10) | 0.0397 (10) | 0.0635 (15) | −0.0022 (8) | −0.0006 (9) | −0.0202 (9) |
O2A | 0.0550 (11) | 0.0627 (12) | 0.0276 (11) | −0.0042 (9) | 0.0155 (9) | 0.0088 (9) |
O3A | 0.0854 (15) | 0.0268 (10) | 0.0315 (11) | −0.0043 (9) | 0.0104 (10) | −0.0007 (8) |
O4A | 0.0536 (11) | 0.0373 (10) | 0.0261 (11) | 0.0004 (8) | 0.0042 (9) | −0.0035 (8) |
N1A | 0.0275 (11) | 0.0427 (12) | 0.0520 (16) | 0.0031 (9) | 0.0068 (10) | 0.0163 (11) |
N2A | 0.0270 (10) | 0.0294 (10) | 0.0280 (12) | −0.0015 (8) | −0.0031 (9) | 0.0067 (10) |
C1A | 0.0287 (14) | 0.0637 (19) | 0.067 (2) | 0.0114 (13) | 0.0020 (14) | 0.0279 (16) |
C2A | 0.0294 (13) | 0.0372 (14) | 0.0305 (15) | 0.0034 (11) | 0.0010 (11) | 0.0061 (11) |
C3A | 0.0271 (12) | 0.0242 (11) | 0.0213 (13) | −0.0004 (9) | 0.0015 (10) | −0.0011 (10) |
C4A | 0.0295 (12) | 0.0239 (12) | 0.0223 (13) | −0.0019 (9) | 0.0007 (10) | −0.0019 (10) |
C5A | 0.0271 (13) | 0.0286 (12) | 0.0388 (16) | −0.0015 (10) | −0.0014 (11) | 0.0032 (11) |
C6A | 0.0427 (16) | 0.0372 (14) | 0.052 (2) | 0.0030 (12) | −0.0096 (14) | 0.0166 (13) |
C7A | 0.0200 (11) | 0.0265 (12) | 0.0297 (15) | 0.0033 (9) | −0.0009 (10) | 0.0040 (10) |
C8A | 0.0251 (11) | 0.0252 (12) | 0.0240 (14) | 0.0013 (9) | −0.0012 (10) | 0.0028 (10) |
C9A | 0.0333 (13) | 0.0342 (13) | 0.0328 (16) | −0.0006 (11) | 0.0035 (11) | 0.0058 (12) |
C10A | 0.0424 (14) | 0.0282 (13) | 0.0372 (17) | −0.0024 (11) | 0.0017 (13) | 0.0120 (12) |
C11A | 0.0386 (14) | 0.0247 (12) | 0.0396 (17) | 0.0033 (10) | 0.0015 (12) | 0.0029 (12) |
C12A | 0.0328 (13) | 0.0284 (13) | 0.0284 (15) | 0.0012 (10) | 0.0023 (11) | −0.0004 (11) |
C13A | 0.0301 (14) | 0.0330 (14) | 0.0279 (16) | −0.0022 (10) | 0.0037 (11) | 0.0006 (11) |
C14A | 0.0494 (16) | 0.0449 (16) | 0.0342 (17) | −0.0054 (12) | 0.0060 (13) | −0.0159 (12) |
S1B | 0.0294 (3) | 0.0277 (3) | 0.0295 (4) | 0.0015 (2) | 0.0053 (3) | 0.0029 (3) |
O1B | 0.0433 (10) | 0.0624 (12) | 0.0284 (12) | 0.0088 (9) | 0.0098 (9) | 0.0041 (10) |
O2B | 0.0416 (10) | 0.0235 (8) | 0.0800 (17) | −0.0027 (7) | 0.0053 (10) | −0.0049 (9) |
O3B | 0.0853 (15) | 0.0260 (9) | 0.0342 (12) | 0.0006 (10) | 0.0057 (11) | 0.0002 (8) |
O4B | 0.0579 (12) | 0.0349 (10) | 0.0257 (12) | −0.0001 (8) | 0.0039 (8) | −0.0017 (8) |
N1B | 0.0273 (11) | 0.0402 (12) | 0.0342 (13) | −0.0019 (9) | 0.0021 (9) | 0.0113 (10) |
N2B | 0.0282 (10) | 0.0297 (9) | 0.0266 (12) | 0.0022 (8) | −0.0006 (9) | 0.0040 (9) |
C1B | 0.0318 (14) | 0.0645 (18) | 0.055 (2) | −0.0014 (13) | −0.0074 (14) | 0.0273 (15) |
C2B | 0.0301 (12) | 0.0297 (12) | 0.0257 (14) | 0.0033 (10) | −0.0003 (10) | 0.0019 (10) |
C3B | 0.0283 (12) | 0.0239 (11) | 0.0208 (13) | 0.0020 (9) | 0.0031 (10) | −0.0003 (10) |
C4B | 0.0281 (11) | 0.0217 (11) | 0.0230 (13) | −0.0006 (9) | 0.0002 (10) | −0.0010 (10) |
C5B | 0.0277 (12) | 0.0356 (13) | 0.0364 (16) | 0.0004 (10) | 0.0000 (11) | 0.0068 (11) |
C6B | 0.0340 (13) | 0.0436 (13) | 0.0417 (19) | 0.0071 (11) | −0.0039 (12) | 0.0145 (13) |
C7B | 0.0215 (11) | 0.0239 (12) | 0.0295 (15) | −0.0005 (9) | −0.0045 (10) | 0.0020 (10) |
C8B | 0.0238 (12) | 0.0240 (12) | 0.0299 (15) | −0.0008 (9) | −0.0002 (10) | 0.0024 (10) |
C9B | 0.0350 (13) | 0.0350 (13) | 0.0254 (15) | 0.0004 (10) | 0.0011 (11) | 0.0061 (11) |
C10B | 0.0433 (15) | 0.0256 (13) | 0.0413 (18) | −0.0019 (11) | −0.0004 (13) | 0.0077 (12) |
C11B | 0.0405 (14) | 0.0223 (12) | 0.0415 (18) | 0.0003 (10) | −0.0050 (12) | 0.0019 (11) |
C12B | 0.0332 (13) | 0.0296 (13) | 0.0311 (16) | 0.0022 (11) | −0.0039 (11) | −0.0003 (11) |
C13B | 0.0261 (12) | 0.0324 (14) | 0.0265 (15) | −0.0028 (10) | 0.0026 (11) | 0.0000 (11) |
C14B | 0.0547 (17) | 0.0465 (16) | 0.0286 (17) | −0.0063 (12) | 0.0051 (13) | −0.0135 (12) |
S1A—O1A | 1.4223 (17) | S1B—O1B | 1.4171 (18) |
S1A—O2A | 1.4233 (19) | S1B—O2B | 1.4247 (17) |
S1A—N1A | 1.578 (2) | S1B—N1B | 1.577 (2) |
S1A—N2A | 1.6781 (18) | S1B—N2B | 1.6793 (19) |
O3A—C13A | 1.204 (3) | O3B—C13B | 1.211 (3) |
O4A—C13A | 1.344 (3) | O4B—C13B | 1.329 (3) |
O4A—C14A | 1.434 (3) | O4B—C14B | 1.453 (3) |
N1A—C2A | 1.326 (3) | N1B—C2B | 1.326 (3) |
N2A—C4A | 1.371 (3) | N2B—C4B | 1.368 (3) |
N2A—C6A | 1.486 (3) | N2B—C6B | 1.480 (3) |
C1A—C2A | 1.496 (3) | C1B—C2B | 1.505 (3) |
C1A—H1A1 | 0.9800 | C1B—H1B1 | 0.9800 |
C1A—H1A2 | 0.9800 | C1B—H1B2 | 0.9800 |
C1A—H1A3 | 0.9800 | C1B—H1B3 | 0.9800 |
C2A—C3A | 1.415 (3) | C2B—C3B | 1.407 (3) |
C3A—C4A | 1.377 (3) | C3B—C4B | 1.383 (3) |
C3A—C7A | 1.502 (3) | C3B—C7B | 1.500 (3) |
C4A—C5A | 1.498 (3) | C4B—C5B | 1.492 (3) |
C5A—H5A1 | 0.9800 | C5B—H5B1 | 0.9800 |
C5A—H5A2 | 0.9800 | C5B—H5B2 | 0.9800 |
C5A—H5A3 | 0.9800 | C5B—H5B3 | 0.9800 |
C6A—H6A1 | 0.9800 | C6B—H6B1 | 0.9800 |
C6A—H6A2 | 0.9800 | C6B—H6B2 | 0.9800 |
C6A—H6A3 | 0.9800 | C6B—H6B3 | 0.9800 |
C7A—C12A | 1.388 (3) | C7B—C12B | 1.391 (3) |
C7A—C8A | 1.420 (3) | C7B—C8B | 1.419 (3) |
C8A—C9A | 1.395 (3) | C8B—C9B | 1.394 (3) |
C8A—C13A | 1.481 (3) | C8B—C13B | 1.493 (3) |
C9A—C10A | 1.389 (4) | C9B—C10B | 1.372 (3) |
C9A—H9A | 0.9500 | C9B—H9B | 0.9500 |
C10A—C11A | 1.376 (3) | C10B—C11B | 1.378 (4) |
C10A—H10A | 0.9500 | C10B—H10B | 0.9500 |
C11A—C12A | 1.381 (3) | C11B—C12B | 1.391 (3) |
C11A—H11A | 0.9500 | C11B—H11B | 0.9500 |
C12A—H12A | 0.9500 | C12B—H12B | 0.9500 |
C14A—H14A | 0.9800 | C14B—H14D | 0.9800 |
C14A—H14B | 0.9800 | C14B—H14E | 0.9800 |
C14A—H14C | 0.9800 | C14B—H14F | 0.9800 |
O1A—S1A—O2A | 115.27 (12) | O1B—S1B—O2B | 115.51 (12) |
O1A—S1A—N1A | 111.17 (13) | O1B—S1B—N1B | 110.67 (11) |
O2A—S1A—N1A | 110.10 (11) | O2B—S1B—N1B | 110.22 (11) |
O1A—S1A—N2A | 107.33 (10) | O1B—S1B—N2B | 107.50 (10) |
O2A—S1A—N2A | 107.39 (11) | O2B—S1B—N2B | 106.78 (9) |
N1A—S1A—N2A | 104.94 (10) | N1B—S1B—N2B | 105.57 (10) |
C13A—O4A—C14A | 116.69 (19) | C13B—O4B—C14B | 116.48 (18) |
C2A—N1A—S1A | 123.12 (16) | C2B—N1B—S1B | 123.38 (17) |
C4A—N2A—C6A | 122.55 (19) | C4B—N2B—C6B | 122.43 (19) |
C4A—N2A—S1A | 121.25 (15) | C4B—N2B—S1B | 122.41 (15) |
C6A—N2A—S1A | 115.74 (15) | C6B—N2B—S1B | 114.83 (16) |
C2A—C1A—H1A1 | 109.5 | C2B—C1B—H1B1 | 109.5 |
C2A—C1A—H1A2 | 109.5 | C2B—C1B—H1B2 | 109.5 |
H1A1—C1A—H1A2 | 109.5 | H1B1—C1B—H1B2 | 109.5 |
C2A—C1A—H1A3 | 109.5 | C2B—C1B—H1B3 | 109.5 |
H1A1—C1A—H1A3 | 109.5 | H1B1—C1B—H1B3 | 109.5 |
H1A2—C1A—H1A3 | 109.5 | H1B2—C1B—H1B3 | 109.5 |
N1A—C2A—C3A | 124.2 (2) | N1B—C2B—C3B | 125.0 (2) |
N1A—C2A—C1A | 114.9 (2) | N1B—C2B—C1B | 114.1 (2) |
C3A—C2A—C1A | 120.9 (2) | C3B—C2B—C1B | 120.9 (2) |
C4A—C3A—C2A | 120.5 (2) | C4B—C3B—C2B | 120.5 (2) |
C4A—C3A—C7A | 120.01 (19) | C4B—C3B—C7B | 120.79 (19) |
C2A—C3A—C7A | 119.01 (19) | C2B—C3B—C7B | 118.7 (2) |
N2A—C4A—C3A | 121.93 (19) | N2B—C4B—C3B | 121.77 (19) |
N2A—C4A—C5A | 114.97 (19) | N2B—C4B—C5B | 115.88 (19) |
C3A—C4A—C5A | 123.1 (2) | C3B—C4B—C5B | 122.3 (2) |
C4A—C5A—H5A1 | 109.5 | C4B—C5B—H5B1 | 109.5 |
C4A—C5A—H5A2 | 109.5 | C4B—C5B—H5B2 | 109.5 |
H5A1—C5A—H5A2 | 109.5 | H5B1—C5B—H5B2 | 109.5 |
C4A—C5A—H5A3 | 109.5 | C4B—C5B—H5B3 | 109.5 |
H5A1—C5A—H5A3 | 109.5 | H5B1—C5B—H5B3 | 109.5 |
H5A2—C5A—H5A3 | 109.5 | H5B2—C5B—H5B3 | 109.5 |
N2A—C6A—H6A1 | 109.5 | N2B—C6B—H6B1 | 109.5 |
N2A—C6A—H6A2 | 109.5 | N2B—C6B—H6B2 | 109.5 |
H6A1—C6A—H6A2 | 109.5 | H6B1—C6B—H6B2 | 109.5 |
N2A—C6A—H6A3 | 109.5 | N2B—C6B—H6B3 | 109.5 |
H6A1—C6A—H6A3 | 109.5 | H6B1—C6B—H6B3 | 109.5 |
H6A2—C6A—H6A3 | 109.5 | H6B2—C6B—H6B3 | 109.5 |
C12A—C7A—C8A | 118.0 (2) | C12B—C7B—C8B | 117.9 (2) |
C12A—C7A—C3A | 118.0 (2) | C12B—C7B—C3B | 118.2 (2) |
C8A—C7A—C3A | 123.9 (2) | C8B—C7B—C3B | 123.80 (19) |
C9A—C8A—C7A | 119.2 (2) | C9B—C8B—C7B | 119.3 (2) |
C9A—C8A—C13A | 118.4 (2) | C9B—C8B—C13B | 119.0 (2) |
C7A—C8A—C13A | 122.4 (2) | C7B—C8B—C13B | 121.7 (2) |
C10A—C9A—C8A | 121.1 (2) | C10B—C9B—C8B | 121.4 (2) |
C10A—C9A—H9A | 119.4 | C10B—C9B—H9B | 119.3 |
C8A—C9A—H9A | 119.4 | C8B—C9B—H9B | 119.3 |
C11A—C10A—C9A | 119.6 (2) | C9B—C10B—C11B | 119.9 (2) |
C11A—C10A—H10A | 120.2 | C9B—C10B—H10B | 120.0 |
C9A—C10A—H10A | 120.2 | C11B—C10B—H10B | 120.0 |
C10A—C11A—C12A | 119.9 (2) | C10B—C11B—C12B | 119.7 (2) |
C10A—C11A—H11A | 120.0 | C10B—C11B—H11B | 120.2 |
C12A—C11A—H11A | 120.0 | C12B—C11B—H11B | 120.2 |
C11A—C12A—C7A | 122.1 (2) | C7B—C12B—C11B | 121.7 (2) |
C11A—C12A—H12A | 118.9 | C7B—C12B—H12B | 119.1 |
C7A—C12A—H12A | 118.9 | C11B—C12B—H12B | 119.1 |
O3A—C13A—O4A | 122.1 (2) | O3B—C13B—O4B | 122.7 (2) |
O3A—C13A—C8A | 126.2 (2) | O3B—C13B—C8B | 125.6 (2) |
O4A—C13A—C8A | 111.7 (2) | O4B—C13B—C8B | 111.7 (2) |
O4A—C14A—H14A | 109.5 | O4B—C14B—H14D | 109.5 |
O4A—C14A—H14B | 109.5 | O4B—C14B—H14E | 109.5 |
H14A—C14A—H14B | 109.5 | H14D—C14B—H14E | 109.5 |
O4A—C14A—H14C | 109.5 | O4B—C14B—H14F | 109.5 |
H14A—C14A—H14C | 109.5 | H14D—C14B—H14F | 109.5 |
H14B—C14A—H14C | 109.5 | H14E—C14B—H14F | 109.5 |
O1A—S1A—N1A—C2A | 95.6 (2) | O1B—S1B—N1B—C2B | 103.6 (2) |
O2A—S1A—N1A—C2A | −135.4 (2) | O2B—S1B—N1B—C2B | −127.4 (2) |
N2A—S1A—N1A—C2A | −20.1 (3) | N2B—S1B—N1B—C2B | −12.5 (2) |
O1A—S1A—N2A—C4A | −96.67 (19) | O1B—S1B—N2B—C4B | −106.12 (19) |
O2A—S1A—N2A—C4A | 138.84 (18) | O2B—S1B—N2B—C4B | 129.36 (19) |
N1A—S1A—N2A—C4A | 21.7 (2) | N1B—S1B—N2B—C4B | 12.1 (2) |
O1A—S1A—N2A—C6A | 75.8 (2) | O1B—S1B—N2B—C6B | 67.42 (19) |
O2A—S1A—N2A—C6A | −48.72 (19) | O2B—S1B—N2B—C6B | −57.1 (2) |
N1A—S1A—N2A—C6A | −165.88 (19) | N1B—S1B—N2B—C6B | −174.41 (18) |
S1A—N1A—C2A—C3A | 8.8 (4) | S1B—N1B—C2B—C3B | 7.2 (4) |
S1A—N1A—C2A—C1A | −172.1 (2) | S1B—N1B—C2B—C1B | −174.6 (2) |
N1A—C2A—C3A—C4A | 5.5 (4) | N1B—C2B—C3B—C4B | 1.3 (4) |
C1A—C2A—C3A—C4A | −173.6 (2) | C1B—C2B—C3B—C4B | −176.7 (2) |
N1A—C2A—C3A—C7A | 177.7 (2) | N1B—C2B—C3B—C7B | −178.7 (2) |
C1A—C2A—C3A—C7A | −1.3 (3) | C1B—C2B—C3B—C7B | 3.2 (3) |
C6A—N2A—C4A—C3A | 176.2 (2) | C6B—N2B—C4B—C3B | −179.1 (2) |
S1A—N2A—C4A—C3A | −11.9 (3) | S1B—N2B—C4B—C3B | −6.1 (3) |
C6A—N2A—C4A—C5A | −2.4 (3) | C6B—N2B—C4B—C5B | 3.4 (3) |
S1A—N2A—C4A—C5A | 169.47 (16) | S1B—N2B—C4B—C5B | 176.44 (17) |
C2A—C3A—C4A—N2A | −3.3 (3) | C2B—C3B—C4B—N2B | −1.6 (3) |
C7A—C3A—C4A—N2A | −175.4 (2) | C7B—C3B—C4B—N2B | 178.5 (2) |
C2A—C3A—C4A—C5A | 175.3 (2) | C2B—C3B—C4B—C5B | 175.7 (2) |
C7A—C3A—C4A—C5A | 3.1 (3) | C7B—C3B—C4B—C5B | −4.2 (3) |
C4A—C3A—C7A—C12A | 96.2 (3) | C4B—C3B—C7B—C12B | −97.4 (3) |
C2A—C3A—C7A—C12A | −76.1 (3) | C2B—C3B—C7B—C12B | 82.7 (3) |
C4A—C3A—C7A—C8A | −86.8 (3) | C4B—C3B—C7B—C8B | 86.7 (3) |
C2A—C3A—C7A—C8A | 100.9 (3) | C2B—C3B—C7B—C8B | −93.2 (3) |
C12A—C7A—C8A—C9A | 0.1 (3) | C12B—C7B—C8B—C9B | −0.1 (3) |
C3A—C7A—C8A—C9A | −177.0 (2) | C3B—C7B—C8B—C9B | 175.9 (2) |
C12A—C7A—C8A—C13A | −178.2 (2) | C12B—C7B—C8B—C13B | 179.3 (2) |
C3A—C7A—C8A—C13A | 4.7 (3) | C3B—C7B—C8B—C13B | −4.7 (3) |
C7A—C8A—C9A—C10A | 0.7 (3) | C7B—C8B—C9B—C10B | 0.2 (3) |
C13A—C8A—C9A—C10A | 179.1 (2) | C13B—C8B—C9B—C10B | −179.2 (2) |
C8A—C9A—C10A—C11A | −0.9 (4) | C8B—C9B—C10B—C11B | −0.1 (4) |
C9A—C10A—C11A—C12A | 0.3 (3) | C9B—C10B—C11B—C12B | −0.1 (4) |
C10A—C11A—C12A—C7A | 0.5 (3) | C8B—C7B—C12B—C11B | −0.1 (3) |
C8A—C7A—C12A—C11A | −0.7 (3) | C3B—C7B—C12B—C11B | −176.3 (2) |
C3A—C7A—C12A—C11A | 176.6 (2) | C10B—C11B—C12B—C7B | 0.2 (4) |
C14A—O4A—C13A—O3A | −2.0 (3) | C14B—O4B—C13B—O3B | 1.7 (3) |
C14A—O4A—C13A—C8A | 179.1 (2) | C14B—O4B—C13B—C8B | −178.6 (2) |
C9A—C8A—C13A—O3A | −161.3 (2) | C9B—C8B—C13B—O3B | 163.0 (2) |
C7A—C8A—C13A—O3A | 16.9 (4) | C7B—C8B—C13B—O3B | −16.5 (4) |
C9A—C8A—C13A—O4A | 17.5 (3) | C9B—C8B—C13B—O4B | −16.7 (3) |
C7A—C8A—C13A—O4A | −164.2 (2) | C7B—C8B—C13B—O4B | 163.9 (2) |
Experimental details
Crystal data | |
Chemical formula | C14H16N2O4S |
Mr | 308.35 |
Crystal system, space group | Orthorhombic, Pna21 |
Temperature (K) | 173 |
a, b, c (Å) | 13.5954 (3), 8.0683 (2), 25.9554 (7) |
V (Å3) | 2847.09 (12) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.25 |
Crystal size (mm) | 0.28 × 0.22 × 0.21 |
Data collection | |
Diffractometer | Nonius KappaCCD diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.935, 0.950 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 33574, 6094, 4522 |
Rint | 0.057 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.037, 0.083, 0.99 |
No. of reflections | 6094 |
No. of parameters | 388 |
No. of restraints | 1 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.21, −0.25 |
Absolute structure | Flack (1983), 2751 Friedel pairs |
Absolute structure parameter | −0.06 (5) |
Computer programs: COLLECT (Nonius, 2000), DENZO-SMN (Otwinowski & Minor, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), OLEX2 (Dolomanov et al., 2009).
Acknowledgements
The authors wish to thank Dr Hong Su from the University of Cape Town for assistance with the data collection and refinement.
References
Bhatt, N., Bhatt, P., Vyas, K. B., Nimavat, K., Govender, T., Kruger, H. G. & Maguire, G. E. M. (2012). Acta Cryst. E68, o2160. CSD CrossRef IUCr Journals Google Scholar
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The synthesis of 1,2,6-thiadiazine-1,1-dioxides derivatives was first reported using sulfamide with alpha and beta diketones (Wright, 1964). We have reported the 3,5-dimethyl based structure with an aromatic ring at position 4 of the thiadiazine ring containing an ethyl ester functional group (Bhatt et al., 2012). The structure displayed intermolecular hydrogen bonding.
The title compound is also a 3,5 dimethyl based structure with an aromatic ring at the same position on the thiadiazine ring, but here the sp3 nitrogen atom is methylated. This prevents any equivalent hydrogen bonding features in the structure seen in previous examples. The is no π-π stacking or weak CH—π inteactions either in the crystal. The title compound has two isomeric forms in the crystal. The sulfur atoms S1A and S1B deviate from their ring planes (N1A/B, C2/AB, C3A/B, C4A/B, N2A/B) by 0.319 (12) Å and 0.182 (12) Å respectively (Fig. 1) and the benzene rings deviate from the planes by 86.8 (3) and 86.7 (3)°, respectively. The ester functional groups of the two isomers are not co-planar to the benzene ring planes but differ by 16.93 (4) and 16.48 (4)°, respectively.