Methyl 2-(3,5-dichloro­phen­yl)-5-dimethyl­amino-3-methyl-1,1-dioxo-1,2,3,4-tetra­hydro-1λ⁶,2,4,6-thia­triazine-3-carboxyl­ate

The title compound, C₁₃H₁₆Cl₂N₄O₄S, was formed by base-assisted N-alkyl­ation of [2-(3,5-dichloro­phen­yl)-1,1-dioxo-2,3-dihydro-1H-1λ⁶-1,2,3,5-thia­triazol-4-yl]dimethyl­amine with methyl 2-bromo­propanoate, followed by a novel base-promoted ring-expansion reaction, to form a relatively rare 1,1-dioxo-1,2,4,6-thia­triazine. The thia­triazine heterocycle adopts an envelope conformation. In the crystal structure, adjacent mol­ecules are linked by an N—H...O hydrogen bond to form chains parallel to the a direction.

Key indicators

• Single-crystal X-ray study
• T = 123 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.043
• wR factor = 0.113
• Data-to-parameter ratio = 18.7

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT318_ALERT_2_C Check Hybridisation of  N3     in Main Residue .          ?
PLAT431_ALERT_2_C Short Inter HL..A Contact  Cl1    ..  O3      ..       3.07 Ang.

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   2 ALERT level C = Check and explain
   0 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
   0 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion

---

Computing details

Data collection: COLLECT (Nonius, 2000); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: SCALEPACK and DENZO (Otwinowski & Minor, 1997); 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).

Methyl 2-(3,5-dichlorophenyl)-5-dimethylamino-3-methyl-1,1-dioxo-1,2,3,4-tetrahydro- 1λ⁶-1,2,4,6-thiatriazine-3-carboxylate

Crystal data

C13H16Cl2N4O4S	Z = 2
Mr = 395.26	F(000) = 408
Triclinic, P1	Dx = 1.541 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.4226 (1) Å	Cell parameters from 14533 reflections
b = 9.7869 (2) Å	θ = 3.5–28.2°
c = 13.9309 (4) Å	µ = 0.53 mm^−1
α = 81.3584 (8)°	T = 123 K
β = 88.7526 (9)°	Acicular, colourless
γ = 79.765 (2)°	0.3 × 0.22 × 0.12 mm
V = 851.93 (3) Å^3

Data collection

Nonius KappaCCD area-detector diffractometer	Rint = 0.029
CCD rotation images, thick slices, ω and φ scans	θmax = 28.2°, θmin = 3.5°
14510 measured reflections	h = −8→8
4122 independent reflections	k = −12→12
3598 reflections with I > 2σ(I)	l = −18→18

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.043	w = 1/[σ^2(Fo^2) + (0.0504P)^2 + 1.1152P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.113	(Δ/σ)max = 0.008
S = 1.04	Δρmax = 0.97 e Å^−3
4122 reflections	Δρmin = −0.71 e Å^−3
221 parameters

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
C1	−0.1236 (3)	0.66058 (19)	0.83790 (13)	0.0148 (4)
C2	−0.1121 (3)	0.60402 (19)	0.67132 (14)	0.0138 (3)
C3	0.0722 (3)	0.35271 (19)	0.72120 (14)	0.0158 (4)
C4	0.2341 (3)	0.2618 (2)	0.68396 (16)	0.0204 (4)
H4	0.3396	0.2976	0.644	0.024*
C5	0.2403 (3)	0.1181 (2)	0.70574 (17)	0.0239 (4)
C6	0.0867 (3)	0.0625 (2)	0.76232 (16)	0.0233 (4)
H6	0.091	−0.036	0.7764	0.028*
C7	−0.0746 (3)	0.1568 (2)	0.79784 (15)	0.0208 (4)
C8	−0.0847 (3)	0.3014 (2)	0.77924 (14)	0.0178 (4)
H8	−0.1951	0.3633	0.8052	0.021*
C9	−0.0460 (3)	0.7366 (2)	0.61104 (14)	0.0159 (4)
C10	0.1526 (4)	0.8174 (2)	0.47716 (16)	0.0280 (5)
H10A	0.0361	0.894	0.4547	0.042*
H10B	0.2282	0.7837	0.421	0.042*
H10C	0.2502	0.8515	0.5171	0.042*
C11	−0.2588 (3)	0.5501 (2)	0.60647 (14)	0.0178 (4)
H11A	−0.3193	0.474	0.6444	0.027*
H11B	−0.178	0.5148	0.5521	0.027*
H11C	−0.3729	0.6268	0.5814	0.027*
C12	−0.1282 (4)	0.7229 (2)	0.99991 (15)	0.0250 (4)
H12A	−0.0447	0.6309	1.0248	0.037*
H12B	−0.2335	0.7515	1.0483	0.037*
H12C	−0.0343	0.7922	0.9868	0.037*
C13	−0.4647 (3)	0.7558 (3)	0.90592 (18)	0.0309 (5)
H13A	−0.5083	0.7999	0.8399	0.046*
H13B	−0.5091	0.8229	0.9512	0.046*
H13C	−0.531	0.6729	0.924	0.046*
Cl1	0.44579 (10)	0.00763 (6)	0.65810 (5)	0.03759 (17)
Cl2	−0.26911 (10)	0.09084 (6)	0.86943 (4)	0.03419 (16)
N1	0.0816 (2)	0.50010 (16)	0.69802 (12)	0.0144 (3)
N2	0.0851 (3)	0.62284 (19)	0.85186 (13)	0.0200 (4)
N3	−0.2256 (2)	0.64237 (17)	0.75777 (12)	0.0159 (3)
H3	−0.3647	0.6541	0.758	0.019*
N4	−0.2360 (3)	0.71399 (19)	0.90983 (12)	0.0193 (3)
O1	0.3183 (2)	0.67376 (15)	0.71171 (11)	0.0205 (3)
O2	0.3894 (2)	0.44597 (15)	0.81466 (11)	0.0221 (3)
O3	−0.1032 (2)	0.85357 (15)	0.62922 (11)	0.0227 (3)
O4	0.0682 (2)	0.70293 (14)	0.53453 (10)	0.0199 (3)
S1	0.23510 (7)	0.56187 (5)	0.77145 (3)	0.01534 (12)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0154 (9)	0.0142 (8)	0.0162 (9)	−0.0061 (7)	0.0003 (7)	−0.0023 (7)
C2	0.0111 (8)	0.0137 (8)	0.0169 (9)	−0.0015 (6)	0.0003 (7)	−0.0044 (7)
C3	0.0150 (9)	0.0126 (8)	0.0199 (9)	−0.0023 (7)	−0.0018 (7)	−0.0031 (7)
C4	0.0164 (9)	0.0171 (9)	0.0275 (10)	−0.0024 (7)	0.0028 (8)	−0.0039 (8)
C5	0.0223 (10)	0.0166 (10)	0.0322 (11)	0.0009 (8)	−0.0013 (8)	−0.0073 (8)
C6	0.0290 (11)	0.0133 (9)	0.0274 (11)	−0.0039 (8)	−0.0057 (9)	−0.0010 (8)
C7	0.0240 (10)	0.0197 (10)	0.0198 (9)	−0.0093 (8)	−0.0020 (8)	−0.0002 (7)
C8	0.0176 (9)	0.0173 (9)	0.0192 (9)	−0.0045 (7)	0.0000 (7)	−0.0036 (7)
C9	0.0139 (9)	0.0153 (9)	0.0183 (9)	−0.0014 (7)	−0.0028 (7)	−0.0028 (7)
C10	0.0419 (13)	0.0222 (11)	0.0215 (10)	−0.0134 (9)	0.0067 (9)	−0.0001 (8)
C11	0.0163 (9)	0.0183 (9)	0.0200 (9)	−0.0028 (7)	−0.0024 (7)	−0.0068 (7)
C12	0.0329 (12)	0.0277 (11)	0.0164 (10)	−0.0080 (9)	−0.0019 (8)	−0.0064 (8)
C13	0.0175 (11)	0.0481 (15)	0.0328 (12)	−0.0076 (10)	0.0068 (9)	−0.0226 (11)
Cl1	0.0339 (3)	0.0192 (3)	0.0583 (4)	0.0028 (2)	0.0104 (3)	−0.0119 (3)
Cl2	0.0420 (4)	0.0267 (3)	0.0368 (3)	−0.0188 (2)	0.0122 (3)	−0.0006 (2)
N1	0.0107 (7)	0.0115 (7)	0.0210 (8)	−0.0019 (6)	−0.0004 (6)	−0.0026 (6)
N2	0.0134 (8)	0.0262 (9)	0.0226 (8)	−0.0048 (6)	−0.0016 (6)	−0.0086 (7)
N3	0.0094 (7)	0.0213 (8)	0.0186 (8)	−0.0028 (6)	0.0012 (6)	−0.0081 (6)
N4	0.0172 (8)	0.0246 (9)	0.0188 (8)	−0.0068 (7)	0.0023 (6)	−0.0084 (7)
O1	0.0154 (7)	0.0190 (7)	0.0280 (8)	−0.0082 (5)	−0.0006 (6)	0.0002 (6)
O2	0.0138 (7)	0.0197 (7)	0.0311 (8)	−0.0003 (5)	−0.0056 (6)	0.0000 (6)
O3	0.0229 (8)	0.0136 (7)	0.0311 (8)	0.0000 (5)	0.0015 (6)	−0.0057 (6)
O4	0.0286 (8)	0.0146 (7)	0.0172 (7)	−0.0063 (6)	0.0052 (6)	−0.0020 (5)
S1	0.0096 (2)	0.0147 (2)	0.0220 (2)	−0.00317 (16)	−0.00136 (16)	−0.00202 (17)

Geometric parameters (Å, º)

C1—N2	1.336 (3)	C10—O4	1.454 (2)
C1—N4	1.338 (2)	C10—H10A	0.98
C1—N3	1.357 (2)	C10—H10B	0.98
C2—N3	1.457 (2)	C10—H10C	0.98
C2—N1	1.476 (2)	C11—H11A	0.98
C2—C11	1.530 (3)	C11—H11B	0.98
C2—C9	1.556 (3)	C11—H11C	0.98
C3—C4	1.389 (3)	C12—N4	1.468 (3)
C3—C8	1.394 (3)	C12—H12A	0.98
C3—N1	1.442 (2)	C12—H12B	0.98
C4—C5	1.387 (3)	C12—H12C	0.98
C4—H4	0.95	C13—N4	1.453 (3)
C5—C6	1.385 (3)	C13—H13A	0.98
C5—Cl1	1.738 (2)	C13—H13B	0.98
C6—C7	1.394 (3)	C13—H13C	0.98
C6—H6	0.95	N1—S1	1.6808 (16)
C7—C8	1.391 (3)	N2—S1	1.5776 (18)
C7—Cl2	1.735 (2)	N3—H3	0.88
C8—H8	0.95	O1—S1	1.4465 (14)
C9—O3	1.201 (2)	O2—S1	1.4327 (14)
C9—O4	1.330 (2)
N2—C1—N4	116.91 (17)	C2—C11—H11A	109.5
N2—C1—N3	123.79 (17)	C2—C11—H11B	109.5
N4—C1—N3	119.25 (17)	H11A—C11—H11B	109.5
N3—C2—N1	110.77 (15)	C2—C11—H11C	109.5
N3—C2—C11	109.67 (15)	H11A—C11—H11C	109.5
N1—C2—C11	111.88 (15)	H11B—C11—H11C	109.5
N3—C2—C9	109.62 (15)	N4—C12—H12A	109.5
N1—C2—C9	108.08 (14)	N4—C12—H12B	109.5
C11—C2—C9	106.70 (15)	H12A—C12—H12B	109.5
C4—C3—C8	120.87 (18)	N4—C12—H12C	109.5
C4—C3—N1	115.87 (17)	H12A—C12—H12C	109.5
C8—C3—N1	123.23 (17)	H12B—C12—H12C	109.5
C5—C4—C3	119.37 (19)	N4—C13—H13A	109.5
C5—C4—H4	120.3	N4—C13—H13B	109.5
C3—C4—H4	120.3	H13A—C13—H13B	109.5
C6—C5—C4	121.7 (2)	N4—C13—H13C	109.5
C6—C5—Cl1	120.22 (16)	H13A—C13—H13C	109.5
C4—C5—Cl1	118.03 (17)	H13B—C13—H13C	109.5
C5—C6—C7	117.40 (18)	C3—N1—C2	120.58 (15)
C5—C6—H6	121.3	C3—N1—S1	115.60 (12)
C7—C6—H6	121.3	C2—N1—S1	110.31 (12)
C8—C7—C6	122.75 (19)	C1—N2—S1	121.62 (14)
C8—C7—Cl2	118.57 (17)	C1—N3—C2	122.02 (16)
C6—C7—Cl2	118.67 (16)	C1—N3—H3	119
C7—C8—C3	117.85 (18)	C2—N3—H3	119
C7—C8—H8	121.1	C1—N4—C13	122.96 (17)
C3—C8—H8	121.1	C1—N4—C12	119.34 (17)
O3—C9—O4	125.60 (18)	C13—N4—C12	117.57 (17)
O3—C9—C2	123.52 (18)	C9—O4—C10	115.38 (16)
O4—C9—C2	110.73 (15)	O2—S1—O1	115.69 (9)
O4—C10—H10A	109.5	O2—S1—N2	110.28 (10)
O4—C10—H10B	109.5	O1—S1—N2	110.10 (9)
H10A—C10—H10B	109.5	O2—S1—N1	107.65 (8)
O4—C10—H10C	109.5	O1—S1—N1	106.09 (8)
H10A—C10—H10C	109.5	N2—S1—N1	106.52 (8)
H10B—C10—H10C	109.5

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3···O1^i	0.88	2.12	2.964 (2)	162

Symmetry code: (i) x−1, y, z.