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

Shafiq, M.; Khan, I.U.; Arshad, M.N.; Mustafa, G.

doi:10.1107/S1600536810045125

organic compounds

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ISSN: 2056-9890

Volume 66| Part 12| December 2010| Page o3109

https://doi.org/10.1107/S1600536810045125

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

Muhammad Shafiq,^a Islam Ullah Khan,^a ^* Muhammad Nadeem Arshad ^a and Ghulam Mustafa ^a

^aMaterials Chemistry Laboratory, Department of Chemistry, GC University, Lahore 54000, Pakistan
^*Correspondence e-mail: iukhan.gcu@gmail.com

(Received 29 October 2010; accepted 3 November 2010; online 10 November 2010)

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, P n a 2₁
a = 14.922 (1) Å
b = 12.1310 (8) Å
c = 7.0811 (4) Å
V = 1281.81 (14) Å³
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[F² > 2σ(F²)] = 0.035
wR(F²) = 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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536810045125/bt5404sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810045125/bt5404Isup2.hkl

checkCIF report

Comment top

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.

Related literature top

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

Experimental top

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

Structure description top

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

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

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); 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 (Spek, 2009).

Figures top

Fig. 1. Perspective view of the title compound with displacement ellipsoids drawn at the 50% probability level.

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

Crystal data top

C₉H₆Br₃NO₃S	F(000) = 848
M_r = 447.94	D_x = 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 top

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

Refinement top

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(F_o²) + (0.0309P)²] where P = (F_o² + 2F_c²)/3
S = 0.99	(Δ/σ)_max = 0.001
2941 reflections	Δρ_max = 0.54 e Å⁻³
156 parameters	Δρ_min = −0.55 e Å⁻³
1 restraint	Absolute structure: Flack (1983), 1242 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.00 (3)

Crystal data top

C₉H₆Br₃NO₃S	V = 1281.81 (14) Å³
M_r = 447.94	Z = 4
Orthorhombic, Pna2₁	Mo Kα radiation
a = 14.922 (1) Å	µ = 9.60 mm⁻¹
b = 12.1310 (8) Å	T = 296 K
c = 7.0811 (4) Å	0.28 × 0.21 × 0.12 mm

Data collection top

Bruker Kappa APEXII CCD diffractometer	2941 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2007)	2221 reflections with I > 2σ(I)
T_min = 0.096, T_max = 0.144	R_int = 0.033
7900 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	H-atom parameters constrained
wR(F²) = 0.071	Δρ_max = 0.54 e Å⁻³
S = 0.99	Δρ_min = −0.55 e Å⁻³
2941 reflections	Absolute structure: Flack (1983), 1242 Friedel pairs
156 parameters	Absolute structure parameter: 0.00 (3)
1 restraint

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
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 (Å²) top

	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, º) top

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)

Experimental details

Crystal data
Chemical formula	C₉H₆Br₃NO₃S
M_r	447.94
Crystal system, space group	Orthorhombic, Pna2₁
Temperature (K)	296
a, b, c (Å)	14.922 (1), 12.1310 (8), 7.0811 (4)
V (Å³)	1281.81 (14)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	9.60
Crystal size (mm)	0.28 × 0.21 × 0.12

Data collection
Diffractometer	Bruker Kappa APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2007)
T_min, T_max	0.096, 0.144
No. of measured, independent and observed [I > 2σ(I)] reflections	7900, 2941, 2221
R_int	0.033
(sin θ/λ)_max (Å⁻¹)	0.666

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.071, 0.99
No. of reflections	2941
No. of parameters	156
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.54, −0.55
Absolute structure	Flack (1983), 1242 Friedel pairs
Absolute structure parameter	0.00 (3)

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2009), WinGX (Farrugia, 1999) and PLATON (Spek, 2009).

Acknowledgements

The authors acknowledge the Higher Education Commission of Pakistan for providing a grant for the project to strengthen the Materials Chemistry Laboratory at GC University Lahore, Pakistan.

References

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