3,3,6-Tribromo-1-methyl-1H-2,1-benzo­thia­zin-4(3H)-one 2,2-dioxide

Abstract

In the title compound, C₉H₆Br₃NO₃S, a halogenated benzothia­zine derivative, the thia­zine ring adopts a sofa conformation. The crystal studied was a racemic twin with a contribution of 72 (1)% of the major domain.

Related literature

For the synthesis and related structures, see: Shafiq et al. (2009a ▶,b ▶).

Experimental

Crystal data

• C₉H₆Br₃NO₃S

• M _r = 447.94

• Orthorhombic,

• a = 14.922 (1) Å

• b = 12.1310 (8) Å

• c = 7.0811 (4) Å

• V = 1281.81 (14) ų

• Z = 4

• Mo Kα radiation

• μ = 9.60 mm⁻¹

• T = 296 K

• 0.28 × 0.21 × 0.12 mm

Data collection

• Bruker Kappa APEXII CCD diffractometer

• Absorption correction: multi-scan (SADABS; Bruker, 2007 ▶) T _min = 0.096, T _max = 0.144

• 7900 measured reflections

• 2941 independent reflections

• 2221 reflections with I > 2σ(I)

• R _int = 0.033

Refinement

• R[F ² > 2σ(F ²)] = 0.035

• wR(F ²) = 0.071

• S = 0.99

• 2941 reflections

• 156 parameters

• 1 restraint

• H-atom parameters constrained

• Δρ_max = 0.54 e Å⁻³

• Δρ_min = −0.55 e Å⁻³

• Absolute structure: Flack (1983 ▶), 1242 Friedel pairs

• Flack parameter: 0.00 (3)

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶) and PLATON (Spek, 2009 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶) and PLATON.

Supplementary Material

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

supplementary crystallographic information

Comment

The title compound, (I), is structurally related to the already reported crystal structures of 3,3-dichloro-1-ethyl-1H-2,1-benzothiazin-4 (3H)-one 2,2-dioxide, (II), (Shafiq et al., 2009a) and 6-bromo-3,3-dichloro-1-methyl-1H-2,1-benzothiazin-4 (3H)-one 2,2-dioxide, (III), (Shafiq et al., 2009b).

Like (II) and (III) the thiazine (C1/C6/C7/C8/S1/N1) ring in the crystal structure adopted a sofa form.

Experimental

The title compound was prepared following the already reported procedure (Shafiq et al., 2009b).

Refinement

All H-atoms were positioned with idealized geometry with C—H = 0.93 Å and C—H = 0.96 Å and were refined using a riding model with U_iso(H) = 1.2 U_eq(C) or U_iso(H) = 1.5 U_eq(C_methyl). The crystal turned out to be a racemic twin with a contribution of 72 (1)% of the major domain.

Figures

Fig. 1.

Perspective view of the title compound with displacement ellipsoids drawn at the 50% probability level.

Crystal data

C9H6Br3NO3S	F(000) = 848
Mr = 447.94	Dx = 2.321 Mg m−3
Orthorhombic, Pna21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2n	Cell parameters from 2326 reflections
a = 14.922 (1) Å	θ = 3.3–24.8°
b = 12.1310 (8) Å	µ = 9.60 mm−1
c = 7.0811 (4) Å	T = 296 K
V = 1281.81 (14) Å3	Needle, light brown
Z = 4	0.28 × 0.21 × 0.12 mm

Data collection

Bruker Kappa APEXII CCD diffractometer	2941 independent reflections
Radiation source: fine-focus sealed tube	2221 reflections with I > 2σ(I)
graphite	Rint = 0.033
φ and ω scans	θmax = 28.2°, θmin = 2.7°
Absorption correction: multi-scan (SADABS; Bruker, 2007)	h = −15→19
Tmin = 0.096, Tmax = 0.144	k = −16→10
7900 measured reflections	l = −8→9

Refinement

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.035	H-atom parameters constrained
wR(F2) = 0.071	w = 1/[σ2(Fo2) + (0.0309P)2] where P = (Fo2 + 2Fc2)/3
S = 0.99	(Δ/σ)max = 0.001
2941 reflections	Δρmax = 0.54 e Å−3
156 parameters	Δρmin = −0.55 e Å−3
1 restraint	Absolute structure: Flack (1983), 1242 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.00 (3)

Special details

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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.

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

	x	y	z	Uiso*/Ueq
Br1	0.56408 (4)	0.70021 (5)	0.24956 (8)	0.05225 (17)
S1	0.21026 (9)	0.32623 (11)	0.3603 (2)	0.0368 (3)
O1	0.2102 (3)	0.6272 (3)	0.2328 (8)	0.0631 (13)
N1	0.3103 (2)	0.3077 (3)	0.2744 (6)	0.0341 (9)
C1	0.3690 (3)	0.3998 (3)	0.2654 (7)	0.0269 (10)
Br2	0.17819 (4)	0.39549 (5)	−0.05254 (9)	0.05073 (17)
O2	0.2124 (3)	0.3737 (3)	0.5431 (5)	0.0505 (11)
C2	0.4609 (3)	0.3843 (3)	0.2690 (8)	0.0352 (11)
H2	0.4841	0.3132	0.2754	0.042*
Br3	0.05403 (4)	0.47720 (5)	0.28558 (9)	0.05946 (19)
O3	0.1596 (3)	0.2288 (3)	0.3279 (6)	0.0569 (11)
C3	0.5178 (3)	0.4721 (4)	0.2632 (8)	0.0385 (11)
H3	0.5794	0.4605	0.2657	0.046*
C4	0.4844 (3)	0.5789 (4)	0.2536 (7)	0.0346 (11)
C5	0.3947 (3)	0.5960 (3)	0.2469 (7)	0.0333 (11)
H5	0.3727	0.6676	0.2400	0.040*
C6	0.3348 (3)	0.5074 (3)	0.2503 (7)	0.0279 (10)
C7	0.2389 (3)	0.5345 (4)	0.2336 (6)	0.0309 (10)
C8	0.1729 (3)	0.4378 (4)	0.2090 (6)	0.0325 (11)
C9	0.3419 (4)	0.1959 (4)	0.2311 (10)	0.0553 (16)
H9C	0.3840	0.1989	0.1287	0.083*
H9B	0.2919	0.1506	0.1958	0.083*
H9A	0.3705	0.1652	0.3405	0.083*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
Br1	0.0503 (4)	0.0549 (3)	0.0516 (3)	−0.0277 (3)	0.0009 (3)	−0.0028 (3)
S1	0.0342 (8)	0.0388 (7)	0.0376 (6)	−0.0059 (6)	0.0022 (6)	0.0082 (6)
O1	0.039 (2)	0.0306 (19)	0.120 (4)	0.0096 (17)	−0.002 (3)	−0.006 (3)
N1	0.029 (2)	0.0234 (19)	0.050 (3)	−0.0030 (16)	0.001 (2)	0.002 (2)
C1	0.031 (3)	0.022 (2)	0.027 (2)	0.0008 (18)	0.004 (2)	0.004 (2)
Br2	0.0663 (4)	0.0518 (3)	0.0341 (2)	0.0025 (3)	−0.0111 (3)	−0.0066 (3)
O2	0.053 (3)	0.069 (3)	0.029 (2)	−0.009 (2)	0.0066 (18)	0.0041 (18)
C2	0.029 (3)	0.029 (2)	0.048 (3)	0.0052 (19)	0.005 (3)	0.007 (3)
Br3	0.0275 (3)	0.0677 (4)	0.0831 (5)	0.0025 (3)	0.0073 (3)	−0.0042 (4)
O3	0.047 (2)	0.043 (2)	0.081 (3)	−0.0203 (19)	0.005 (2)	0.009 (2)
C3	0.025 (3)	0.049 (3)	0.041 (3)	0.000 (2)	0.002 (3)	0.002 (3)
C4	0.031 (3)	0.039 (3)	0.033 (2)	−0.012 (2)	0.000 (2)	0.000 (3)
C5	0.041 (3)	0.022 (2)	0.037 (3)	−0.0056 (19)	0.001 (2)	−0.002 (2)
C6	0.029 (3)	0.028 (2)	0.027 (2)	−0.0008 (18)	0.000 (2)	−0.001 (2)
C7	0.030 (3)	0.028 (2)	0.034 (2)	−0.001 (2)	0.000 (2)	−0.001 (2)
C8	0.025 (3)	0.039 (3)	0.033 (3)	0.000 (2)	0.001 (2)	−0.007 (2)
C9	0.063 (4)	0.027 (3)	0.076 (4)	−0.002 (3)	0.014 (4)	−0.006 (3)

Geometric parameters (Å, °)

Br1—C4	1.892 (4)	C2—H2	0.9300
S1—O2	1.417 (4)	Br3—C8	1.916 (5)
S1—O3	1.422 (4)	C3—C4	1.390 (6)
S1—N1	1.627 (4)	C3—H3	0.9300
S1—C8	1.814 (5)	C4—C5	1.356 (7)
O1—C7	1.204 (5)	C5—C6	1.398 (6)
N1—C1	1.421 (5)	C5—H5	0.9300
N1—C9	1.469 (6)	C6—C7	1.473 (6)
C1—C2	1.384 (6)	C7—C8	1.542 (6)
C1—C6	1.406 (5)	C9—H9C	0.9600
Br2—C8	1.923 (4)	C9—H9B	0.9600
C2—C3	1.362 (6)	C9—H9A	0.9600
O2—S1—O3	119.9 (2)	C4—C5—C6	120.9 (4)
O2—S1—N1	112.1 (2)	C4—C5—H5	119.6
O3—S1—N1	108.2 (2)	C6—C5—H5	119.6
O2—S1—C8	104.1 (2)	C5—C6—C1	118.9 (4)
O3—S1—C8	111.2 (2)	C5—C6—C7	116.6 (4)
N1—S1—C8	99.4 (2)	C1—C6—C7	124.5 (4)
C1—N1—C9	121.2 (4)	O1—C7—C6	123.7 (4)
C1—N1—S1	118.3 (3)	O1—C7—C8	118.9 (4)
C9—N1—S1	120.0 (3)	C6—C7—C8	117.4 (4)
C2—C1—C6	119.2 (4)	C7—C8—S1	107.7 (3)
C2—C1—N1	120.3 (4)	C7—C8—Br3	111.7 (3)
C6—C1—N1	120.6 (4)	S1—C8—Br3	107.7 (2)
C3—C2—C1	120.7 (4)	C7—C8—Br2	106.6 (3)
C3—C2—H2	119.6	S1—C8—Br2	110.9 (2)
C1—C2—H2	119.6	Br3—C8—Br2	112.2 (2)
C2—C3—C4	120.5 (4)	N1—C9—H9C	109.5
C2—C3—H3	119.8	N1—C9—H9B	109.5
C4—C3—H3	119.8	H9C—C9—H9B	109.5
C5—C4—C3	119.9 (4)	N1—C9—H9A	109.5
C5—C4—Br1	120.1 (4)	H9C—C9—H9A	109.5
C3—C4—Br1	120.0 (4)	H9B—C9—H9A	109.5
O2—S1—N1—C1	−54.7 (4)	C2—C1—C6—C7	176.2 (5)
O3—S1—N1—C1	170.9 (4)	N1—C1—C6—C7	−3.0 (7)
C8—S1—N1—C1	54.8 (4)	C5—C6—C7—O1	−6.2 (8)
O2—S1—N1—C9	117.5 (5)	C1—C6—C7—O1	175.1 (5)
O3—S1—N1—C9	−16.9 (5)	C5—C6—C7—C8	171.7 (4)
C8—S1—N1—C9	−133.0 (5)	C1—C6—C7—C8	−7.1 (7)
C9—N1—C1—C2	−18.4 (7)	O1—C7—C8—S1	−142.5 (5)
S1—N1—C1—C2	153.6 (4)	C6—C7—C8—S1	39.5 (5)
C9—N1—C1—C6	160.7 (5)	O1—C7—C8—Br3	−24.5 (6)
S1—N1—C1—C6	−27.2 (6)	C6—C7—C8—Br3	157.6 (3)
C6—C1—C2—C3	1.8 (8)	O1—C7—C8—Br2	98.3 (5)
N1—C1—C2—C3	−179.1 (5)	C6—C7—C8—Br2	−79.6 (4)
C1—C2—C3—C4	0.0 (8)	O2—S1—C8—C7	57.1 (4)
C2—C3—C4—C5	−1.1 (8)	O3—S1—C8—C7	−172.5 (3)
C2—C3—C4—Br1	179.0 (4)	N1—S1—C8—C7	−58.7 (3)
C3—C4—C5—C6	0.3 (8)	O2—S1—C8—Br3	−63.5 (3)
Br1—C4—C5—C6	−179.8 (4)	O3—S1—C8—Br3	66.9 (3)
C4—C5—C6—C1	1.6 (7)	N1—S1—C8—Br3	−179.3 (2)
C4—C5—C6—C7	−177.3 (4)	O2—S1—C8—Br2	173.4 (3)
C2—C1—C6—C5	−2.6 (7)	O3—S1—C8—Br2	−56.2 (3)
N1—C1—C6—C5	178.3 (4)	N1—S1—C8—Br2	57.6 (3)