(4-Bromo­phen­yl)(5-dimethyl­amino-1,1-dioxo-2-phenyl-1,2-dihydro-1λ⁶,2,4,6-thia­triazin-3-yl)­methanone

The title compound, C₁₇H₁₅BrN₄O₃S, was formed by base-assisted N-alkyl­ation of (1,1-dioxo-2-phenyl-2,3-dihydro-1H-1λ⁶,2,3,5-thia­triazol-4-yl)dimethyl­amine with p-bromo­phen­acyl bromide, followed by ring expansion and aerial oxidation to form an unusual 5-acyl-substituted 3-amino-1,1-dioxo-1,2,4,6-thia­triazine. The thiatriazine ring adopts an envelope conformation, with the S atom displaced by 0.308 (2) Å from the plane of the other five atoms.

Key indicators

• Single-crystal X-ray study
• T = 123 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.034
• wR factor = 0.087
• Data-to-parameter ratio = 17.2

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT369_ALERT_2_C Long   C(sp2)-C(sp2) Bond  C1     -   C3     ...       1.53 Ang.
PLAT431_ALERT_2_C Short Inter HL..A Contact  Br1    ..  O3      ..       3.22 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
   0 ALERT type 5 Informative message, check

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Computing details

Data collection: COLLECT (Nonius, 2000); cell refinement: DENZO–SMN (Otwinowski & Minor, 1997); data reduction: X-SEED (Barbour, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: X-SEED and POV-RAY (Persistence of Vision, 2004); software used to prepare material for publication: WinGX (Farrugia, 1999).

(4-Bromophenyl)(5-dimethylamino-1,1-dioxo-2-phenyl-1,2-dihydro- 1λ⁶,2,4,6-thiatriazin-3-yl)methanone

Crystal data

C17H15BrN4O3S	F(000) = 1760
Mr = 435.3	Dx = 1.631 Mg m^−3
Monoclinic, C2/c	Melting point: 428 K
Hall symbol: -C 2yc	Mo Kα radiation, λ = 0.71073 Å
a = 23.4478 (3) Å	Cell parameters from 21515 reflections
b = 10.0971 (2) Å	θ = 0.4–29.6°
c = 15.2847 (2) Å	µ = 2.46 mm^−1
β = 101.518 (1)°	T = 123 K
V = 3545.85 (10) Å^3	Block, colourless
Z = 8	0.25 × 0.25 × 0.1 mm

Data collection

Nonius KappaCCD diffractometer	3411 reflections with I > 2σ(I)
1° frames in φ and ω scans	Rint = 0.042
Absorption correction: empirical (using intensity measurements) (SORTAV; Otwinowski & Minor, 1997)	θmax = 27.5°, θmin = 1.8°
Tmin = 0.578, Tmax = 0.791	h = −30→30
18424 measured reflections	k = −13→13
4071 independent reflections	l = −19→19

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.035	w = 1/[σ^2(Fo^2) + (0.044P)^2 + 4.5742P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.087	(Δ/σ)max = 0.001
S = 1.05	Δρmax = 1.15 e Å^−3
4071 reflections	Δρmin = −0.60 e Å^−3
237 parameters

Special details

Experimental. 1H NMR(CDCl3, 400?MHz, δ, p.p.m.) 7.70(2H, d, J=8.8?Hz, ArH), 7.60(2H, d, J=8.8?Hz, ArH), 7.27–7.36(5H, m, ArH), 3.24(3H, s, CH3—N), 3.23(3H, s, CH3—N). 13 C NMR(CDCl3, 50?MHz, δ, p.p.m.) 184.3, 158.8, 157.3, 132.4, 132.2, 131.8, 131.0, 130.9, 130.3, 129.6, 129.2, 37.7, 37.5. m/z (APCI,+ve, MeOH: CH3CN:H2O 2:1:1) 435, 437 (M+1). Analysis, calculated for C17H15BrN4O3S: C 46.91, H 3.47, N 12.87, S 7.37%. found: C 47.17, H 3.53, N 12.89, S 7.08%. m.p. 427–429?K.

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.

Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane)

11.5572 (0.0185) x + 8.6350 (0.0052) y + 0.8964 (0.0136) z = 3.2977 (0.0026)

* -0.0262 (0.0010) N2 * 0.0351 (0.0014) C2 * -0.0130 (0.0013) N3 * -0.0149 (0.0014) C1 * 0.0190 (0.0010) N1 - 0.3079 (0.0022) S1

Rms deviation of fitted atoms = 0.0231

14.8751 (0.0195) x + 6.8790 (0.0100) y + 3.5339 (0.0194) z = 4.0750 (0.0041)

Angle to previous plane (with approximate e.s.d.) = 17.47 (0.14)

* 0.0000 (0.0000) N2 * 0.0000 (0.0000) S1 * 0.0000 (0.0000) N1

Rms deviation of fitted atoms = 0.0000

11.2163 (0.0176) x + 8.4520 (0.0050) y + 2.5164 (0.0118) z = 3.2865 (0.0028)

Angle to previous plane (with approximate e.s.d.) = 13.90 (0.15)

* 0.0253 (0.0013) N2 * -0.0235 (0.0013) N3 * -0.0077 (0.0018) C2 * 0.0162 (0.0018) N4 * 0.0183 (0.0013) C16 * -0.0286 (0.0012) C17

Rms deviation of fitted atoms = 0.0211

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.

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

	x	y	z	Uiso*/Ueq
Br1	0.028605 (11)	0.86351 (2)	0.124090 (18)	0.02963 (10)
S1	0.21099 (2)	0.04553 (5)	0.17637 (4)	0.01704 (13)
O1	0.18796 (7)	−0.08450 (16)	0.18409 (11)	0.0244 (4)
O2	0.26191 (7)	0.07917 (17)	0.24062 (10)	0.0229 (4)
O3	0.02529 (7)	0.18241 (17)	0.13212 (12)	0.0272 (4)
N1	0.15759 (8)	0.15331 (17)	0.19136 (12)	0.0179 (4)
N2	0.21947 (8)	0.07684 (19)	0.07974 (12)	0.0204 (4)
N3	0.13013 (8)	0.20240 (18)	0.03683 (12)	0.0178 (4)
N4	0.19020 (8)	0.15663 (18)	−0.06136 (12)	0.0181 (4)
C1	0.12216 (9)	0.2044 (2)	0.11842 (14)	0.0163 (4)
C2	0.18025 (10)	0.1426 (2)	0.02070 (15)	0.0172 (4)
C3	0.06374 (9)	0.2613 (2)	0.13006 (14)	0.0181 (4)
C4	0.05642 (10)	0.4068 (2)	0.13125 (15)	0.0183 (4)
C5	0.00018 (10)	0.4591 (2)	0.11523 (18)	0.0269 (5)
H5	−0.0324	0.4013	0.106	0.032*
C6	−0.00818 (11)	0.5939 (2)	0.11274 (19)	0.0300 (6)
H6	−0.0464	0.6297	0.0998	0.036*
C7	0.03997 (11)	0.6772 (2)	0.12937 (15)	0.0229 (5)
C8	0.09632 (10)	0.6279 (2)	0.14851 (15)	0.0202 (5)
H8	0.1287	0.6861	0.1616	0.024*
C9	0.10425 (10)	0.4920 (2)	0.14814 (15)	0.0188 (5)
H9	0.1425	0.4565	0.1595	0.023*
C10	0.14928 (9)	0.1735 (2)	0.28200 (14)	0.0169 (4)
C11	0.18390 (10)	0.2672 (2)	0.33372 (16)	0.0243 (5)
H11	0.2103	0.3199	0.309	0.029*
C12	0.17929 (11)	0.2827 (2)	0.42197 (17)	0.0297 (6)
H12	0.2024	0.3472	0.4581	0.036*
C13	0.14131 (11)	0.2047 (3)	0.45790 (16)	0.0273 (5)
H13	0.1391	0.2141	0.519	0.033*
C14	0.10635 (10)	0.1125 (2)	0.40482 (17)	0.0247 (5)
H14	0.0796	0.0606	0.4294	0.03*
C15	0.11032 (10)	0.0960 (2)	0.31654 (16)	0.0196 (5)
H15	0.0867	0.0326	0.2801	0.023*
C16	0.15046 (11)	0.2303 (2)	−0.13086 (15)	0.0253 (5)
H16A	0.1105	0.2002	−0.1332	0.038*
H16B	0.1611	0.2147	−0.1888	0.038*
H16C	0.1533	0.3251	−0.117	0.038*
C17	0.24079 (10)	0.0914 (2)	−0.08552 (15)	0.0210 (5)
H17A	0.2747	0.1021	−0.0368	0.031*
H17B	0.249	0.1316	−0.1401	0.031*
H17C	0.2325	−0.0031	−0.0958	0.031*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Br1	0.03008 (15)	0.01636 (13)	0.04118 (17)	0.00559 (10)	0.00403 (11)	−0.00394 (10)
S1	0.0161 (3)	0.0158 (3)	0.0201 (3)	0.0041 (2)	0.0057 (2)	0.0027 (2)
O1	0.0276 (9)	0.0156 (8)	0.0327 (10)	0.0017 (7)	0.0126 (7)	0.0029 (7)
O2	0.0181 (8)	0.0293 (9)	0.0214 (8)	0.0037 (7)	0.0039 (7)	0.0020 (7)
O3	0.0190 (8)	0.0190 (8)	0.0437 (11)	−0.0016 (7)	0.0064 (8)	0.0002 (7)
N1	0.0174 (9)	0.0177 (9)	0.0192 (9)	0.0048 (7)	0.0053 (7)	0.0014 (7)
N2	0.0208 (10)	0.0200 (10)	0.0214 (10)	0.0079 (8)	0.0068 (8)	0.0020 (8)
N3	0.0162 (9)	0.0172 (9)	0.0202 (10)	0.0013 (7)	0.0043 (7)	0.0006 (7)
N4	0.0194 (9)	0.0183 (9)	0.0177 (9)	0.0021 (7)	0.0061 (8)	−0.0002 (7)
C1	0.0136 (10)	0.0126 (10)	0.0228 (12)	−0.0006 (8)	0.0038 (8)	0.0000 (8)
C2	0.0180 (11)	0.0124 (10)	0.0217 (11)	−0.0015 (8)	0.0049 (9)	−0.0022 (8)
C3	0.0158 (10)	0.0198 (11)	0.0185 (11)	0.0015 (9)	0.0028 (9)	−0.0008 (9)
C4	0.0192 (11)	0.0175 (10)	0.0188 (11)	0.0016 (9)	0.0049 (9)	−0.0015 (9)
C5	0.0168 (11)	0.0224 (12)	0.0413 (15)	0.0002 (9)	0.0051 (10)	−0.0051 (11)
C6	0.0173 (12)	0.0230 (12)	0.0482 (16)	0.0057 (10)	0.0031 (11)	−0.0060 (11)
C7	0.0285 (13)	0.0147 (10)	0.0257 (13)	0.0049 (9)	0.0059 (10)	−0.0035 (9)
C8	0.0209 (11)	0.0186 (11)	0.0215 (12)	−0.0020 (9)	0.0050 (9)	−0.0015 (9)
C9	0.0162 (10)	0.0206 (11)	0.0204 (11)	0.0031 (9)	0.0057 (9)	0.0006 (9)
C10	0.0175 (10)	0.0152 (10)	0.0185 (11)	0.0046 (8)	0.0049 (9)	0.0007 (8)
C11	0.0254 (12)	0.0199 (11)	0.0286 (13)	−0.0052 (10)	0.0077 (10)	−0.0009 (10)
C12	0.0363 (14)	0.0248 (13)	0.0270 (13)	−0.0032 (11)	0.0039 (11)	−0.0062 (10)
C13	0.0335 (14)	0.0308 (13)	0.0188 (12)	0.0085 (11)	0.0082 (10)	−0.0014 (10)
C14	0.0196 (11)	0.0287 (13)	0.0289 (13)	0.0039 (10)	0.0124 (10)	0.0047 (10)
C15	0.0156 (11)	0.0177 (10)	0.0256 (12)	0.0001 (9)	0.0046 (9)	−0.0006 (9)
C16	0.0282 (13)	0.0292 (13)	0.0185 (12)	0.0057 (10)	0.0052 (10)	0.0032 (10)
C17	0.0226 (12)	0.0213 (11)	0.0212 (12)	0.0024 (9)	0.0096 (9)	−0.0021 (9)

Geometric parameters (Å, º)

Br1—C7	1.899 (2)	C7—C8	1.387 (3)
S1—O2	1.4272 (17)	C8—C9	1.385 (3)
S1—O1	1.4335 (17)	C8—H8	0.95
S1—N2	1.5614 (19)	C9—H9	0.95
S1—N1	1.7087 (18)	C10—C15	1.385 (3)
O3—C3	1.209 (3)	C10—C11	1.387 (3)
N1—C1	1.352 (3)	C11—C12	1.383 (3)
N1—C10	1.451 (3)	C11—H11	0.95
N2—C2	1.330 (3)	C12—C13	1.382 (4)
N3—C1	1.298 (3)	C12—H12	0.95
N3—C2	1.386 (3)	C13—C14	1.389 (4)
N4—C2	1.328 (3)	C13—H13	0.95
N4—C17	1.467 (3)	C14—C15	1.381 (3)
N4—C16	1.468 (3)	C14—H14	0.95
C1—C3	1.528 (3)	C15—H15	0.95
C3—C4	1.479 (3)	C16—H16A	0.98
C4—C5	1.396 (3)	C16—H16B	0.98
C4—C9	1.396 (3)	C16—H16C	0.98
C5—C6	1.375 (3)	C17—H17A	0.98
C5—H5	0.95	C17—H17B	0.98
C6—C7	1.390 (3)	C17—H17C	0.98
C6—H6	0.95
O2—S1—O1	116.01 (10)	C9—C8—H8	120.7
O2—S1—N2	110.84 (10)	C7—C8—H8	120.7
O1—S1—N2	112.61 (10)	C8—C9—C4	120.5 (2)
O2—S1—N1	106.91 (10)	C8—C9—H9	119.7
O1—S1—N1	105.91 (9)	C4—C9—H9	119.7
N2—S1—N1	103.48 (9)	C15—C10—C11	121.6 (2)
C1—N1—C10	123.78 (18)	C15—C10—N1	120.6 (2)
C1—N1—S1	118.57 (15)	C11—C10—N1	117.71 (19)
C10—N1—S1	117.32 (14)	C12—C11—C10	118.8 (2)
C2—N2—S1	122.78 (16)	C12—C11—H11	120.6
C1—N3—C2	117.87 (19)	C10—C11—H11	120.6
C2—N4—C17	119.53 (19)	C13—C12—C11	120.3 (2)
C2—N4—C16	122.12 (18)	C13—C12—H12	119.8
C17—N4—C16	118.27 (18)	C11—C12—H12	119.8
N3—C1—N1	127.14 (19)	C12—C13—C14	120.1 (2)
N3—C1—C3	114.97 (18)	C12—C13—H13	119.9
N1—C1—C3	117.70 (18)	C14—C13—H13	119.9
N4—C2—N2	117.77 (19)	C15—C14—C13	120.3 (2)
N4—C2—N3	115.86 (19)	C15—C14—H14	119.9
N2—C2—N3	126.3 (2)	C13—C14—H14	119.9
O3—C3—C4	124.4 (2)	C14—C15—C10	118.8 (2)
O3—C3—C1	116.5 (2)	C14—C15—H15	120.6
C4—C3—C1	118.95 (18)	C10—C15—H15	120.6
C5—C4—C9	119.7 (2)	N4—C16—H16A	109.5
C5—C4—C3	118.8 (2)	N4—C16—H16B	109.5
C9—C4—C3	121.6 (2)	H16A—C16—H16B	109.5
C6—C5—C4	120.2 (2)	N4—C16—H16C	109.5
C6—C5—H5	119.9	H16A—C16—H16C	109.5
C4—C5—H5	119.9	H16B—C16—H16C	109.5
C5—C6—C7	119.2 (2)	N4—C17—H17A	109.5
C5—C6—H6	120.4	N4—C17—H17B	109.5
C7—C6—H6	120.4	H17A—C17—H17B	109.5
C8—C7—C6	121.7 (2)	N4—C17—H17C	109.5
C8—C7—Br1	118.94 (18)	H17A—C17—H17C	109.5
C6—C7—Br1	119.32 (18)	H17B—C17—H17C	109.5
C9—C8—C7	118.5 (2)
O2—S1—N1—C1	138.49 (16)	O3—C3—C4—C5	−13.9 (4)
O1—S1—N1—C1	−97.24 (17)	C1—C3—C4—C5	161.2 (2)
N2—S1—N1—C1	21.41 (19)	O3—C3—C4—C9	165.9 (2)
O2—S1—N1—C10	−47.84 (18)	C1—C3—C4—C9	−19.0 (3)
O1—S1—N1—C10	76.43 (17)	C9—C4—C5—C6	2.4 (4)
N2—S1—N1—C10	−164.92 (16)	C3—C4—C5—C6	−177.7 (2)
O2—S1—N2—C2	−131.98 (19)	C4—C5—C6—C7	−2.2 (4)
O1—S1—N2—C2	96.20 (19)	C5—C6—C7—C8	0.0 (4)
N1—S1—N2—C2	−17.7 (2)	C5—C6—C7—Br1	179.0 (2)
C2—N3—C1—N1	−0.3 (3)	C6—C7—C8—C9	2.0 (4)
C2—N3—C1—C3	−175.08 (18)	Br1—C7—C8—C9	−177.04 (17)
C10—N1—C1—N3	172.2 (2)	C7—C8—C9—C4	−1.7 (3)
S1—N1—C1—N3	−14.6 (3)	C5—C4—C9—C8	−0.5 (3)
C10—N1—C1—C3	−13.2 (3)	C3—C4—C9—C8	179.7 (2)
S1—N1—C1—C3	160.03 (15)	C1—N1—C10—C15	82.2 (3)
C17—N4—C2—N2	4.7 (3)	S1—N1—C10—C15	−91.1 (2)
C16—N4—C2—N2	−178.4 (2)	C1—N1—C10—C11	−101.3 (3)
C17—N4—C2—N3	−177.18 (19)	S1—N1—C10—C11	85.4 (2)
C16—N4—C2—N3	−0.3 (3)	C15—C10—C11—C12	0.3 (4)
S1—N2—C2—N4	−175.90 (16)	N1—C10—C11—C12	−176.2 (2)
S1—N2—C2—N3	6.2 (3)	C10—C11—C12—C13	0.8 (4)
C1—N3—C2—N4	−172.18 (19)	C11—C12—C13—C14	−1.7 (4)
C1—N3—C2—N2	5.7 (3)	C12—C13—C14—C15	1.6 (4)
N3—C1—C3—O3	95.5 (2)	C13—C14—C15—C10	−0.5 (3)
N1—C1—C3—O3	−79.7 (3)	C11—C10—C15—C14	−0.4 (3)
N3—C1—C3—C4	−80.0 (3)	N1—C10—C15—C14	175.9 (2)
N1—C1—C3—C4	104.7 (2)