Crystal structure of 1-bromo-4-methane­sulfonyl-2,3-di­methyl­benzene

Dai, S.; Wang, Y.

doi:10.1107/S205698901502099X

organic compounds

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ISSN: 2056-9890

Volume 71| Part 12| December 2015| Page o973

https://doi.org/10.1107/S205698901502099X

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Crystal structure of 1-bromo-4-methanesulfonyl-2,3-dimethylbenzene

Shangwei Dai ^a and Yifeng Wang ^a ^*

^aZhejiang Key Laboratory of Green Pesticides and Cleaner Production Technology, Zhejiang University of Technology, Hangzhou 310014, People's Republic of China
^*Correspondence e-mail: wangyifeng@zjut.edu.cn

Edited by S. Parkin, University of Kentucky, USA (Received 28 October 2015; accepted 5 November 2015; online 21 November 2015)

The title compound, C₉H₁₁BrO₂S, is an important intermediate in the synthesis of the herbicide Topramezone. In the crystal, there are weak intermolecular Br⋯O interactions of 3.286 (4) Å. The dihedral angle between the plane of the benzene ring and that defined by the O—S—O atoms of the methanesulfonyl group is 49.06 (3)°.

Keywords: crystal structure; sulfonyl; Topramezone; intermediate; Br⋯O interactions.

CCDC reference: 1435173

1. Related literature

For general background information, including the synthesis of the title compound, see: Joachim et al. (2007 , 2011 ).

2. Experimental

2.1. Crystal data

C₉H₁₁BrO₂S
M_r = 263.15
Monoclinic, P 2₁ /c
a = 8.808 (8) Å
b = 5.247 (5) Å
c = 22.66 (2) Å
β = 100.956 (15)°
V = 1028.0 (16) Å³
Z = 4
Mo Kα radiation
μ = 4.17 mm⁻¹
T = 296 K
0.21 × 0.17 × 0.13 mm

2.2. Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Krause et al., 2015 ) T_min = 0.475, T_max = 0.613
4866 measured reflections
1809 independent reflections
1263 reflections with I > 2σ(I)
R_int = 0.030

2.3. Refinement

R[F² > 2σ(F²)] = 0.041
wR(F²) = 0.111
S = 1.07
1809 reflections
121 parameters
H-atom parameters constrained
Δρ_max = 0.64 e Å⁻³
Δρ_min = −0.48 e Å⁻³

Data collection: APEX2 (Bruker, 2000 ); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

CCDC reference: 1435173

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S205698901502099X/pk2567sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S205698901502099X/pk2567Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S205698901502099X/pk2567Isup3.cml

checkCIF report

Comment top

The title compound, C₉H₁₁O₂SBr, was readily synthesized by the oxidation of 1-bromo-2,3-dimethyl-4-(methylthio)benzene using H₂O₂ as the oxidizing agent and Na₂WO₄ as catalyst. This compound is an intermediate in the synthesis of Topramezone. In this article, the crystal structure of the title compound is presented (Figs. 1 & 2). In the crystal, there are weak intermolecular Br···O interactions between Br1 and O2 of a symmetry-related [(1 + x, 1 + y, z)] molecule, with a Br···O distance of 3.286 (4) Å. The dihedral angle between the benzene ring and the plane defined by the three atoms (O—S—O) of the methanesulfonyl group is 49.06 (3)°. The bond angle of the O—S—O group is 117.11 (3)°, and the distance between the two oxygen atoms is 2.432 (2) Å.

Related literature top

For general background information, including the synthesis of the title compound, see: Joachim et al. (2007, 2011).

Experimental top

In a reaction flask, 1-bromo-2,3-dimethyl-4-(methylthio)-benzene (0.03 mol, 4.56 g), and Na₂WO₄ (0.68 mmol, 0.20 g) were added in acetic acid (10 ml). The mixture was stirred and heated to 100°C, then H₂O₂ (0.09 mol, 10.2 g, 30%) was added dropwise over a period of 1 h. After the reaction was complete (monitored by GC—MS), the mixture was cooled to room temperature and poured into ice water (100 ml) and stirred for 0.5 h, and then filtered. The filtered cake was washed with water (10 ml) and dried to give yellow solid. Single crystals were obtained by slow evaporation of a dichloromethane solution.

Structure description top

For general background information, including the synthesis of the title compound, see: Joachim et al. (2007, 2011).

Computing details top

Data collection: APEX2 (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The structure of the title compound. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. The crystal packing of the title compound viewed down the b axis.

1-Bromo-4-methanesulfonyl-2,3-dimethylbenzene top

Crystal data top

C₉H₁₁BrO₂S	F(000) = 528
M_r = 263.15	D_x = 1.700 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1424 reflections
a = 8.808 (8) Å	θ = 2.7–24.0°
b = 5.247 (5) Å	µ = 4.17 mm⁻¹
c = 22.66 (2) Å	T = 296 K
β = 100.956 (15)°	Block, yellow
V = 1028.0 (16) Å³	0.21 × 0.17 × 0.13 mm
Z = 4

Data collection top

Bruker APEXII CCD diffractometer	1809 independent reflections
Radiation source: fine-focus sealed tube	1263 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.030
φ and ω scans	θ_max = 25.0°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	h = −8→10
T_min = 0.475, T_max = 0.613	k = −6→6
4866 measured reflections	l = −26→26

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.111	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.0594P)² + 0.1157P] where P = (F_o² + 2F_c²)/3
1809 reflections	(Δ/σ)_max = 0.001
121 parameters	Δρ_max = 0.64 e Å⁻³
0 restraints	Δρ_min = −0.48 e Å⁻³

Crystal data top

C₉H₁₁BrO₂S	V = 1028.0 (16) Å³
M_r = 263.15	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 8.808 (8) Å	µ = 4.17 mm⁻¹
b = 5.247 (5) Å	T = 296 K
c = 22.66 (2) Å	0.21 × 0.17 × 0.13 mm
β = 100.956 (15)°

Data collection top

Bruker APEXII CCD diffractometer	1809 independent reflections
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	1263 reflections with I > 2σ(I)
T_min = 0.475, T_max = 0.613	R_int = 0.030
4866 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.041	0 restraints
wR(F²) = 0.111	H-atom parameters constrained
S = 1.07	Δρ_max = 0.64 e Å⁻³
1809 reflections	Δρ_min = −0.48 e Å⁻³
121 parameters

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Br1	1.20567 (5)	1.24921 (9)	0.36104 (2)	0.0774 (3)
S1	0.64891 (11)	0.56778 (19)	0.41420 (4)	0.0485 (3)
C4	0.7962 (4)	0.7560 (6)	0.39287 (15)	0.0392 (9)
C6	0.8938 (4)	1.0673 (7)	0.33261 (14)	0.0391 (8)
C1	1.0328 (4)	1.0524 (7)	0.37228 (16)	0.0450 (9)
C5	0.7718 (4)	0.9127 (6)	0.34188 (14)	0.0354 (8)
O2	0.5621 (3)	0.4403 (6)	0.36349 (13)	0.0748 (9)
O1	0.7180 (4)	0.4133 (7)	0.46413 (14)	0.0822 (10)
C9	0.5306 (6)	0.7918 (8)	0.4399 (2)	0.0679 (13)
H9A	0.4920	0.9096	0.4082	0.102*
H9B	0.5893	0.8827	0.4734	0.102*
H9C	0.4455	0.7065	0.4523	0.102*
C8	0.6225 (4)	0.9180 (8)	0.29757 (16)	0.0528 (10)
H8A	0.5540	0.7908	0.3081	0.079*
H8B	0.6418	0.8837	0.2580	0.079*
H8C	0.5757	1.0831	0.2981	0.079*
C3	0.9363 (5)	0.7514 (7)	0.43240 (18)	0.0551 (11)
H3	0.9490	0.6483	0.4664	0.066*
C2	1.0550 (4)	0.8967 (9)	0.42176 (19)	0.0601 (11)
H2	1.1505	0.8910	0.4477	0.072*
C7	0.8704 (6)	1.2484 (7)	0.28001 (19)	0.0602 (12)
H7A	0.9538	1.3692	0.2852	0.090*
H7B	0.7742	1.3373	0.2778	0.090*
H7C	0.8683	1.1543	0.2435	0.090*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0506 (3)	0.0762 (4)	0.1110 (5)	−0.0200 (2)	0.0293 (3)	0.0004 (3)
S1	0.0482 (5)	0.0414 (6)	0.0613 (6)	−0.0039 (4)	0.0240 (5)	0.0013 (5)
C4	0.0371 (19)	0.041 (2)	0.042 (2)	−0.0012 (16)	0.0123 (16)	−0.0033 (17)
C6	0.045 (2)	0.035 (2)	0.0399 (19)	0.0051 (17)	0.0152 (16)	−0.0030 (17)
C1	0.0328 (19)	0.047 (2)	0.057 (2)	−0.0052 (16)	0.0142 (17)	−0.002 (2)
C5	0.0373 (18)	0.0315 (19)	0.0385 (19)	0.0038 (16)	0.0096 (15)	−0.0045 (16)
O2	0.0742 (19)	0.065 (2)	0.090 (2)	−0.0315 (16)	0.0290 (17)	−0.0260 (18)
O1	0.082 (2)	0.077 (2)	0.093 (2)	0.0011 (18)	0.0300 (18)	0.0428 (19)
C9	0.064 (3)	0.061 (3)	0.090 (3)	0.000 (2)	0.044 (3)	−0.011 (2)
C8	0.047 (2)	0.053 (3)	0.053 (2)	0.0019 (19)	−0.0024 (18)	0.002 (2)
C3	0.047 (2)	0.064 (3)	0.052 (2)	0.005 (2)	0.0045 (19)	0.017 (2)
C2	0.037 (2)	0.073 (3)	0.066 (3)	0.001 (2)	0.0010 (19)	0.009 (2)
C7	0.076 (3)	0.047 (3)	0.063 (3)	0.001 (2)	0.026 (2)	0.013 (2)

Geometric parameters (Å, º) top

Br1—C1	1.896 (4)	C9—H9A	0.9600
S1—O2	1.421 (3)	C9—H9B	0.9600
S1—O1	1.430 (3)	C9—H9C	0.9600
S1—C9	1.743 (4)	C8—H8A	0.9600
S1—C4	1.770 (3)	C8—H8B	0.9600
C4—C5	1.401 (5)	C8—H8C	0.9600
C4—C3	1.380 (5)	C3—C2	1.352 (5)
C6—C1	1.377 (5)	C3—H3	0.9300
C6—C5	1.393 (5)	C2—H2	0.9300
C6—C7	1.508 (5)	C7—H7A	0.9600
C1—C2	1.371 (5)	C7—H7B	0.9600
C5—C8	1.496 (5)	C7—H7C	0.9600

O2—S1—O1	117.1 (2)	S1—C9—H9C	109.5
O2—S1—C9	108.9 (2)	H9A—C9—H9C	109.5
O1—S1—C9	108.0 (2)	H9B—C9—H9C	109.5
O2—S1—C4	110.59 (17)	C5—C8—H8A	109.5
O1—S1—C4	107.95 (19)	C5—C8—H8B	109.5
C9—S1—C4	103.3 (2)	H8A—C8—H8B	109.5
C5—C4—C3	121.6 (3)	C5—C8—H8C	109.5
C5—C4—S1	123.2 (3)	H8A—C8—H8C	109.5
C3—C4—S1	115.1 (3)	H8B—C8—H8C	109.5
C1—C6—C5	119.0 (3)	C2—C3—C4	120.0 (4)
C1—C6—C7	121.5 (3)	C2—C3—H3	120.0
C5—C6—C7	119.5 (3)	C4—C3—H3	120.0
C6—C1—C2	122.6 (3)	C3—C2—C1	119.1 (4)
C6—C1—Br1	121.2 (3)	C3—C2—H2	120.4
C2—C1—Br1	116.2 (3)	C1—C2—H2	120.4
C4—C5—C6	117.6 (3)	C6—C7—H7A	109.5
C4—C5—C8	122.8 (3)	C6—C7—H7B	109.5
C6—C5—C8	119.5 (3)	H7A—C7—H7B	109.5
S1—C9—H9A	109.5	C6—C7—H7C	109.5
S1—C9—H9B	109.5	H7A—C7—H7C	109.5
H9A—C9—H9B	109.5	H7B—C7—H7C	109.5

O2—S1—C4—C5	44.6 (3)	C3—C4—C5—C8	178.7 (4)
O1—S1—C4—C5	173.9 (3)	S1—C4—C5—C8	−5.7 (4)
C9—S1—C4—C5	−71.8 (3)	C1—C6—C5—C4	2.3 (5)
O2—S1—C4—C3	−139.5 (3)	C7—C6—C5—C4	−177.0 (3)
O1—S1—C4—C3	−10.2 (3)	C1—C6—C5—C8	−177.2 (3)
C9—S1—C4—C3	104.1 (3)	C7—C6—C5—C8	3.5 (5)
C5—C6—C1—C2	−2.0 (5)	C5—C4—C3—C2	−1.3 (6)
C7—C6—C1—C2	177.3 (4)	S1—C4—C3—C2	−177.3 (3)
C5—C6—C1—Br1	178.0 (2)	C4—C3—C2—C1	1.7 (6)
C7—C6—C1—Br1	−2.7 (5)	C6—C1—C2—C3	−0.1 (6)
C3—C4—C5—C6	−0.7 (5)	Br1—C1—C2—C3	180.0 (3)
S1—C4—C5—C6	174.9 (2)

Experimental details

Crystal data
Chemical formula	C₉H₁₁BrO₂S
M_r	263.15
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	8.808 (8), 5.247 (5), 22.66 (2)
β (°)	100.956 (15)
V (Å³)	1028.0 (16)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	4.17
Crystal size (mm)	0.21 × 0.17 × 0.13

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Krause et al., 2015)
T_min, T_max	0.475, 0.613
No. of measured, independent and observed [I > 2σ(I)] reflections	4866, 1809, 1263
R_int	0.030
(sin θ/λ)_max (Å⁻¹)	0.594

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.111, 1.07
No. of reflections	1809
No. of parameters	121
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.64, −0.48

Computer programs: APEX2 (Bruker, 2000), SAINT (Bruker, 2000), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), XP in SHELXTL (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Acknowledgements

We acknowledge the financial support of Zhejiang Key Course of Chemical Engineering and Technology, Zhejiang University of Technology.

References

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