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

Abstract

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)°.

Related literature  

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

Experimental  

Crystal data  

• C₉H₁₁BrO₂S

• M _r = 263.15

• Monoclinic,

• a = 8.808 (8) Å

• b = 5.247 (5) Å

• c = 22.66 (2) Å

• β = 100.956 (15)°

• V = 1028.0 (16) ų

• Z = 4

• Mo Kα radiation

• μ = 4.17 mm⁻¹

• T = 296 K

• 0.21 × 0.17 × 0.13 mm

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

Refinement  

• R[F ² > 2σ(F ²)] = 0.041

• wR(F ²) = 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.

Supplementary Material

CCDC reference: 1435173

Additional supporting information: crystallographic information; 3D view; checkCIF report

supplementary crystallographic information

S1. Comment

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.

S2. Experimental

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.

S3. Refinement

All H atoms were placed at calculated positions and allowed to ride on their parent atoms, with C—H = 0.93–0.96 Å and U_iso(H) = 1.2 or 1.5U_eq (C).

Figures

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.

Crystal data

C9H11BrO2S	F(000) = 528
Mr = 263.15	Dx = 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

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

Refinement

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(Fo2) + (0.0594P)2 + 0.1157P] where P = (Fo2 + 2Fc2)/3
1809 reflections	(Δ/σ)max = 0.001
121 parameters	Δρmax = 0.64 e Å−3
0 restraints	Δρmin = −0.48 e Å−3

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.

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	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 (Ų)

	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)

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)