Ethyl 2-(3,5-dimethyl-1,1-dioxo-2H-1λ(6),2,6-thia-diazin-4-yl)benzoate.

In the title compound, C(14)H(16)N(2)O(4)S, the thia-diazine ring is in a half-boat conformation. The aromatic ring deviates from the plane of this moiety at an angle of 74.6 (2)°. The structure displays inter-molecular N-H⋯O hydrogen bonding [N⋯O = 2.8157 (16) Å], creating ribbons along the [010] axis. There are also weak C-H⋯O inter-actions in the crystal but no π-π stacking.

Related literature

For the synthesis of 1,2,6-thia­diazine-1,1-dioxide derivatives, see: Wright (1964 ▶); Ochoa & Stud (1978 ▶). For the biological activity of 1,2,6-thia­diazine-1,1-dioxide derivatives, see: Aran et al. (1986 ▶); Herrero et al. (1992 ▶); Breining et al. (1995 ▶); Campillo et al. (2000 ▶). For related structures, see: Elguero et al. (1982 ▶).

Experimental

Crystal data

C14H16N2O4S

M = 308.35

Monoclinic,

a = 10.3943 (2) Å

b = 6.6089 (2) Å

c = 10.6563 (3) Å

β = 94.982 (2)°

V = 729.27 (3) Å3

Z = 2

Mo Kα radiation

μ = 0.24 mm−1

T = 173 K

0.25 × 0.24 × 0.23 mm

Data collection

Nonius KappaCCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2006 ▶) T min = 0.943, T max = 0.947

3321 measured reflections

3321 independent reflections

3083 reflections with I > 2σ(I)

R int = 0.013

Refinement

R[F 2 > 2σ(F 2)] = 0.027

wR(F 2) = 0.067

S = 1.08

3321 reflections

198 parameters

2 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.22 e Å−3

Δρmin = −0.22 e Å−3

Absolute structure: Flack (1983 ▶) 1512 Friedel pairs

Flack parameter: −0.03 (5)

Data collection: COLLECT (Nonius, 2000 ▶); cell refinement: 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.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812024907/hg5223sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812024907/hg5223Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536812024907/hg5223Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C14H16N2O4S	F(000) = 324
Mr = 308.35	Dx = 1.404 Mg m−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 3321 reflections
a = 10.3943 (2) Å	θ = 3.6–27.5°
b = 6.6089 (2) Å	µ = 0.24 mm−1
c = 10.6563 (3) Å	T = 173 K
β = 94.982 (2)°	Block, colourless
V = 729.27 (3) Å3	0.25 × 0.24 × 0.23 mm
Z = 2

Nonius KappaCCD diffractometer	3321 independent reflections
Radiation source: fine-focus sealed tube	3083 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.013
1.2° φ scans and ω scans	θmax = 27.5°, θmin = 3.6°
Absorption correction: multi-scan (SADABS; Bruker, 2006)	h = −13→13
Tmin = 0.943, Tmax = 0.947	k = −8→8
3321 measured reflections	l = −13→13

Refinement on F2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F2 > 2σ(F2)] = 0.027	w = 1/[σ2(Fo2) + (0.0356P)2 + 0.1059P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.067	(Δ/σ)max < 0.001
S = 1.08	Δρmax = 0.22 e Å−3
3321 reflections	Δρmin = −0.22 e Å−3
198 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
2 restraints	Extinction coefficient: 0.021 (3)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983) ???? Friedel pairs
Secondary atom site location: difference Fourier map	Flack parameter: −0.03 (5)

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	0.22417 (3)	0.66320 (6)	−0.19373 (3)	0.02436 (10)
O1	0.32997 (11)	0.7730 (2)	−0.23716 (11)	0.0362 (3)
O2	0.13244 (11)	0.58238 (18)	−0.28774 (10)	0.0343 (3)
O3	0.07360 (10)	0.52605 (18)	0.21011 (10)	0.0305 (3)
O4	0.04265 (9)	0.69099 (17)	0.38957 (9)	0.0245 (2)
N1	0.14372 (11)	0.81211 (19)	−0.10443 (11)	0.0228 (3)
H1	0.0717 (13)	0.887 (3)	−0.1454 (17)	0.049 (6)*
N2	0.27760 (12)	0.4887 (2)	−0.09828 (12)	0.0287 (3)
C1	0.11769 (16)	1.0140 (3)	0.07966 (15)	0.0323 (4)
H1A	0.0268	0.9787	0.0850	0.048*
H1B	0.1233	1.1368	0.0288	0.048*
H1C	0.1591	1.0381	0.1645	0.048*
C2	0.18463 (13)	0.8442 (2)	0.01961 (13)	0.0209 (3)
C3	0.27298 (13)	0.7164 (2)	0.08085 (13)	0.0206 (3)
C4	0.30819 (13)	0.5334 (2)	0.02143 (14)	0.0244 (3)
C5	0.37968 (18)	0.3714 (3)	0.09778 (16)	0.0377 (4)
H5A	0.4693	0.4140	0.1186	0.057*
H5B	0.3784	0.2457	0.0489	0.057*
H5C	0.3380	0.3487	0.1756	0.057*
C6	0.32137 (14)	0.7514 (2)	0.21576 (13)	0.0226 (3)
C7	0.24812 (13)	0.7118 (2)	0.31791 (12)	0.0207 (3)
C8	0.30187 (14)	0.7466 (2)	0.44105 (13)	0.0243 (3)
H8	0.2517	0.7216	0.5098	0.029*
C9	0.42703 (15)	0.8167 (3)	0.46405 (14)	0.0284 (3)
H9	0.4634	0.8364	0.5481	0.034*
C10	0.49884 (15)	0.8579 (3)	0.36372 (15)	0.0313 (4)
H10	0.5843	0.9086	0.3788	0.038*
C11	0.44671 (14)	0.8255 (3)	0.24139 (14)	0.0296 (3)
H11	0.4973	0.8543	0.1734	0.036*
C12	0.11380 (13)	0.6337 (2)	0.29881 (12)	0.0222 (3)
C13	−0.08984 (13)	0.6165 (2)	0.38507 (14)	0.0269 (3)
H13A	−0.0908	0.4668	0.3881	0.032*
H13B	−0.1394	0.6610	0.3064	0.032*
C14	−0.14763 (15)	0.7028 (3)	0.49745 (14)	0.0309 (4)
H14A	−0.1467	0.8509	0.4928	0.046*
H14B	−0.0971	0.6586	0.5745	0.046*
H14C	−0.2369	0.6554	0.4986	0.046*

	U11	U22	U33	U12	U13	U23
S1	0.02388 (17)	0.0332 (2)	0.01587 (16)	0.00301 (16)	0.00125 (11)	−0.00161 (15)
O1	0.0280 (6)	0.0546 (7)	0.0272 (6)	−0.0033 (5)	0.0091 (5)	0.0012 (5)
O2	0.0371 (6)	0.0418 (7)	0.0223 (5)	0.0019 (5)	−0.0074 (5)	−0.0080 (5)
O3	0.0283 (5)	0.0411 (7)	0.0221 (5)	−0.0120 (5)	0.0017 (4)	−0.0079 (5)
O4	0.0196 (4)	0.0317 (6)	0.0224 (5)	−0.0035 (4)	0.0033 (4)	−0.0038 (5)
N1	0.0220 (6)	0.0292 (7)	0.0169 (6)	0.0044 (5)	0.0001 (4)	0.0016 (5)
N2	0.0318 (7)	0.0337 (7)	0.0203 (6)	0.0090 (6)	0.0013 (5)	−0.0023 (5)
C1	0.0378 (9)	0.0303 (9)	0.0288 (8)	0.0088 (7)	0.0025 (7)	−0.0046 (7)
C2	0.0210 (7)	0.0248 (7)	0.0170 (7)	−0.0015 (6)	0.0030 (5)	−0.0003 (6)
C3	0.0184 (6)	0.0282 (8)	0.0153 (6)	−0.0006 (5)	0.0016 (5)	0.0006 (5)
C4	0.0204 (7)	0.0310 (8)	0.0217 (7)	0.0042 (6)	0.0025 (5)	0.0026 (6)
C5	0.0416 (10)	0.0385 (10)	0.0317 (9)	0.0143 (8)	−0.0046 (7)	0.0036 (7)
C6	0.0218 (7)	0.0278 (7)	0.0178 (7)	0.0009 (6)	−0.0002 (5)	0.0017 (6)
C7	0.0218 (6)	0.0225 (8)	0.0175 (6)	−0.0007 (5)	−0.0007 (5)	−0.0009 (5)
C8	0.0278 (7)	0.0284 (8)	0.0164 (7)	−0.0008 (6)	0.0009 (5)	−0.0006 (6)
C9	0.0286 (8)	0.0337 (8)	0.0216 (7)	−0.0037 (7)	−0.0051 (6)	−0.0019 (6)
C10	0.0230 (7)	0.0416 (10)	0.0282 (8)	−0.0078 (7)	−0.0042 (6)	0.0004 (7)
C11	0.0232 (7)	0.0420 (9)	0.0238 (8)	−0.0039 (7)	0.0027 (6)	0.0016 (7)
C12	0.0240 (7)	0.0255 (8)	0.0169 (6)	−0.0020 (6)	0.0010 (5)	0.0023 (6)
C13	0.0201 (7)	0.0315 (9)	0.0290 (8)	−0.0046 (6)	0.0016 (5)	−0.0024 (6)
C14	0.0263 (7)	0.0362 (10)	0.0310 (8)	−0.0025 (6)	0.0062 (6)	−0.0002 (7)

S1—O2	1.4255 (11)	C5—H5B	0.9800
S1—O1	1.4279 (12)	C5—H5C	0.9800
S1—N2	1.6046 (14)	C6—C11	1.396 (2)
S1—N1	1.6466 (12)	C6—C7	1.406 (2)
O3—C12	1.2269 (17)	C7—C8	1.3998 (18)
O4—C12	1.3229 (17)	C7—C12	1.4859 (19)
O4—C13	1.4593 (16)	C8—C9	1.383 (2)
N1—C2	1.3694 (18)	C8—H8	0.9500
N1—H1	0.9697 (10)	C9—C10	1.383 (2)
N2—C4	1.3210 (19)	C9—H9	0.9500
C1—C2	1.494 (2)	C10—C11	1.384 (2)
C1—H1A	0.9800	C10—H10	0.9500
C1—H1B	0.9800	C11—H11	0.9500
C1—H1C	0.9800	C13—C14	1.498 (2)
C2—C3	1.3707 (19)	C13—H13A	0.9900
C3—C4	1.427 (2)	C13—H13B	0.9900
C3—C6	1.4992 (19)	C14—H14A	0.9800
C4—C5	1.502 (2)	C14—H14B	0.9800
C5—H5A	0.9800	C14—H14C	0.9800
O2—S1—O1	116.72 (7)	C11—C6—C3	118.12 (13)
O2—S1—N2	110.47 (7)	C7—C6—C3	123.68 (13)
O1—S1—N2	109.69 (7)	C8—C7—C6	119.76 (13)
O2—S1—N1	106.73 (7)	C8—C7—C12	118.63 (12)
O1—S1—N1	109.12 (7)	C6—C7—C12	121.60 (12)
N2—S1—N1	103.20 (6)	C9—C8—C7	120.93 (13)
C12—O4—C13	117.73 (11)	C9—C8—H8	119.5
C2—N1—S1	121.31 (10)	C7—C8—H8	119.5
C2—N1—H1	121.2 (12)	C8—C9—C10	119.44 (14)
S1—N1—H1	117.2 (12)	C8—C9—H9	120.3
C4—N2—S1	119.50 (11)	C10—C9—H9	120.3
C2—C1—H1A	109.5	C9—C10—C11	120.28 (14)
C2—C1—H1B	109.5	C9—C10—H10	119.9
H1A—C1—H1B	109.5	C11—C10—H10	119.9
C2—C1—H1C	109.5	C10—C11—C6	121.38 (14)
H1A—C1—H1C	109.5	C10—C11—H11	119.3
H1B—C1—H1C	109.5	C6—C11—H11	119.3
N1—C2—C3	120.21 (13)	O3—C12—O4	123.68 (12)
N1—C2—C1	114.38 (13)	O3—C12—C7	124.07 (13)
C3—C2—C1	125.23 (13)	O4—C12—C7	112.25 (11)
C2—C3—C4	119.86 (13)	O4—C13—C14	106.74 (11)
C2—C3—C6	121.10 (13)	O4—C13—H13A	110.4
C4—C3—C6	118.59 (13)	C14—C13—H13A	110.4
N2—C4—C3	124.64 (13)	O4—C13—H13B	110.4
N2—C4—C5	115.46 (14)	C14—C13—H13B	110.4
C3—C4—C5	119.84 (13)	H13A—C13—H13B	108.6
C4—C5—H5A	109.5	C13—C14—H14A	109.5
C4—C5—H5B	109.5	C13—C14—H14B	109.5
H5A—C5—H5B	109.5	H14A—C14—H14B	109.5
C4—C5—H5C	109.5	C13—C14—H14C	109.5
H5A—C5—H5C	109.5	H14A—C14—H14C	109.5
H5B—C5—H5C	109.5	H14B—C14—H14C	109.5
C11—C6—C7	118.20 (13)
O2—S1—N1—C2	151.55 (12)	C2—C3—C6—C7	74.6 (2)
O1—S1—N1—C2	−81.50 (13)	C4—C3—C6—C7	−97.68 (17)
N2—S1—N1—C2	35.09 (13)	C11—C6—C7—C8	−0.2 (2)
O2—S1—N2—C4	−146.56 (12)	C3—C6—C7—C8	179.14 (14)
O1—S1—N2—C4	83.40 (13)	C11—C6—C7—C12	179.72 (14)
N1—S1—N2—C4	−32.79 (13)	C3—C6—C7—C12	−0.9 (2)
S1—N1—C2—C3	−16.62 (19)	C6—C7—C8—C9	−0.9 (2)
S1—N1—C2—C1	167.96 (11)	C12—C7—C8—C9	179.14 (14)
N1—C2—C3—C4	−9.2 (2)	C7—C8—C9—C10	1.7 (2)
C1—C2—C3—C4	165.70 (14)	C8—C9—C10—C11	−1.2 (3)
N1—C2—C3—C6	178.59 (13)	C9—C10—C11—C6	0.1 (3)
C1—C2—C3—C6	−6.5 (2)	C7—C6—C11—C10	0.6 (2)
S1—N2—C4—C3	13.8 (2)	C3—C6—C11—C10	−178.75 (15)
S1—N2—C4—C5	−169.16 (12)	C13—O4—C12—O3	1.8 (2)
C2—C3—C4—N2	11.2 (2)	C13—O4—C12—C7	−177.25 (12)
C6—C3—C4—N2	−176.42 (14)	C8—C7—C12—O3	−150.10 (15)
C2—C3—C4—C5	−165.74 (14)	C6—C7—C12—O3	30.0 (2)
C6—C3—C4—C5	6.7 (2)	C8—C7—C12—O4	28.97 (19)
C2—C3—C6—C11	−106.03 (17)	C6—C7—C12—O4	−150.95 (13)
C4—C3—C6—C11	81.65 (18)	C12—O4—C13—C14	179.87 (12)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O3i	0.97 (2)	1.85 (2)	2.8157 (16)	175 (2)
C5—H5A···O1ii	0.98	2.52	3.310 (2)	137

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O3i	0.97 (2)	1.85 (2)	2.8157 (16)	175 (2)
C5—H5A⋯O1ii	0.98	2.52	3.310 (2)	137

Symmetry codes: (i) ; (ii) .