2-Methyl­sulfonyl-4-(trifluoro­meth­yl)benzoic acid

Yao, L.-S.; We, B.; Gao, J.-S.

doi:10.1107/S160053681202243X

organic compounds

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Volume 68| Part 6| June 2012| Page o1856

doi:10.1107/S160053681202243X

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2-Methylsulfonyl-4-(trifluoromethyl)benzoic acid

Lin-Shan Yao,^a Bo We ^a and Jin-Sheng Gao ^a ^*

^aEngineering Research Center of Pesticides of Heilongjiang University, Heilongjiang University, Harbin 150050, People's Republic of China
^*Correspondence e-mail: hgf1000@163.com

(Received 7 May 2012; accepted 17 May 2012; online 23 May 2012)

In the title molecule, C₉H₇F₃O₄S, the S and the methyl C atoms of the methylsulfonyl group deviate from the benzene ring plane by 0.185 (2) and −1.394 (3) Å, respectively. In the crystal, O—H⋯O hydrogen bonds link the molecules into chains along [201]. Weak C—H⋯O interactions further link these chains into layers parallel to the ac plane.

Related literature

For details of the synthesis, see: Cain et al. (1998 ).

Experimental

Crystal data

C₉H₇F₃O₄S
M_r = 268.21
Monoclinic, P 2₁ /c
a = 5.0804 (10) Å
b = 17.345 (4) Å
c = 11.576 (2) Å
β = 95.41 (3)°
V = 1015.6 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.36 mm⁻¹
T = 293 K
0.39 × 0.32 × 0.22 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.871, T_max = 0.926
9132 measured reflections
2250 independent reflections
1879 reflections with I > 2σ(I)
R_int = 0.029

Refinement

R[F² > 2σ(F²)] = 0.044
wR(F²) = 0.123
S = 1.11
2250 reflections
158 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.39 e Å⁻³
Δρ_min = −0.38 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2⋯O4ⁱ	0.82 (1)	1.92 (1)	2.725 (3)	169 (4)
C9—H9B⋯O3ⁱⁱ	0.96	2.35	3.208 (3)	148
Symmetry codes: (i) $[x-1, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (ii) x+1, y, z.

Data collection: RAPID-AUTO (Rigaku, 1998 ); cell refinement: RAPID-AUTO; data reduction: CrystalClear (Rigaku/MSC, 2002 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053681202243X/cv5300sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681202243X/cv5300Isup2.hkl

Supporting information file. DOI: 10.1107/S160053681202243X/cv5300Isup3.cml

checkCIF report

Comment top

The title compound, (I), is a intermediate in the synthesis of sulfonylurea herbicides developed and produced by E. I. du Pont de Nemours and Company. Herein, we report its crystal structure.

In (I) (Fig. 1), the S and the methyl C atoms of the methylsulfonyl group deviate from the benzene ring plane at 0.185 (2) and -1.394 (3) Å, respectively. Intermoleculear O—H···O hydrogen bonds (Table 1) link the molecules into chains along [201] (Fig. 2), and weak C—H···O interactions (Table 1) link further these chains into layers parallel to ac plane.

Related literature top

For details of the synthesis, see: Cain et al. (1998).

Experimental top

The title compound was prepared by the reaction of 2-(methylsulphenyl)-4-trifluoromethylbenzoic acid and hydrogen peroxide in acetic acid at 10 ° (Cain et al., 1998). A colourless crystal suitable for single-crystal X-ray diffraction was obtained by the recrystallization from dichloromethane.

Computing details top

Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-AUTO (Rigaku, 1998); data reduction: CrystalClear (Rigaku/MSC, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of (I) showing displacement ellipsoids at the 50% probability level for non-H atoms.
	Fig. 2. A portion of the crystal packing showing hydrogen-bonded (dashed lines) chains.

2-Methylsulfonyl-4-(trifluoromethyl)benzoic acid top

Crystal data top

C₉H₇F₃O₄S	F(000) = 544
M_r = 268.21	D_x = 1.754 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 8167 reflections
a = 5.0804 (10) Å	θ = 3.0–27.5°
b = 17.345 (4) Å	µ = 0.36 mm⁻¹
c = 11.576 (2) Å	T = 293 K
β = 95.41 (3)°	Block, colorless
V = 1015.6 (4) Å³	0.39 × 0.32 × 0.22 mm
Z = 4

Data collection top

Rigaku R-AXIS RAPID diffractometer	2250 independent reflections
Radiation source: fine-focus sealed tube	1879 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.029
ω scan	θ_max = 27.5°, θ_min = 3.5°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −6→6
T_min = 0.871, T_max = 0.926	k = −22→22
9132 measured reflections	l = −14→14

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)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.123	H atoms treated by a mixture of independent and constrained refinement
S = 1.11	w = 1/[σ²(F_o²) + (0.0555P)² + 0.7827P] where P = (F_o² + 2F_c²)/3
2250 reflections	(Δ/σ)_max = 0.001
158 parameters	Δρ_max = 0.39 e Å⁻³
1 restraint	Δρ_min = −0.38 e Å⁻³

Crystal data top

C₉H₇F₃O₄S	V = 1015.6 (4) Å³
M_r = 268.21	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 5.0804 (10) Å	µ = 0.36 mm⁻¹
b = 17.345 (4) Å	T = 293 K
c = 11.576 (2) Å	0.39 × 0.32 × 0.22 mm
β = 95.41 (3)°

Data collection top

Rigaku R-AXIS RAPID diffractometer	2250 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	1879 reflections with I > 2σ(I)
T_min = 0.871, T_max = 0.926	R_int = 0.029
9132 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.044	1 restraint
wR(F²) = 0.123	H atoms treated by a mixture of independent and constrained refinement
S = 1.11	Δρ_max = 0.39 e Å⁻³
2250 reflections	Δρ_min = −0.38 e Å⁻³
158 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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
C1	0.2822 (5)	0.85011 (13)	0.09229 (19)	0.0319 (5)
C2	0.4291 (5)	0.80387 (12)	0.17524 (19)	0.0284 (5)
C3	0.6265 (5)	0.83602 (13)	0.25122 (19)	0.0304 (5)
H3	0.7242	0.8051	0.3051	0.037*
C4	0.6780 (5)	0.91494 (13)	0.2467 (2)	0.0337 (5)
C5	0.5314 (5)	0.96140 (14)	0.1677 (2)	0.0392 (6)
H5	0.5636	1.0141	0.1658	0.047*
C6	0.3360 (5)	0.92880 (14)	0.0911 (2)	0.0396 (6)
H6	0.2386	0.9602	0.0378	0.048*
C7	0.0778 (5)	0.81875 (14)	0.0022 (2)	0.0353 (5)
C8	0.8793 (5)	0.94984 (14)	0.3342 (2)	0.0389 (6)
C9	0.4951 (5)	0.65356 (15)	0.0879 (2)	0.0436 (6)
H9A	0.4715	0.5992	0.0984	0.065*
H9B	0.6803	0.6649	0.0889	0.065*
H9C	0.4062	0.6691	0.0147	0.065*
F1	1.0869 (4)	0.90478 (10)	0.35927 (19)	0.0655 (5)
F2	0.7743 (4)	0.96498 (13)	0.43239 (16)	0.0743 (6)
F3	0.9734 (4)	1.01622 (10)	0.29917 (18)	0.0648 (5)
O1	0.0598 (4)	0.75293 (11)	−0.02770 (17)	0.0511 (5)
O2	−0.0822 (4)	0.87346 (13)	−0.0433 (2)	0.0594 (6)
H2	−0.187 (6)	0.853 (2)	−0.092 (3)	0.089*
O3	0.0826 (3)	0.69334 (11)	0.19817 (16)	0.0409 (4)
O4	0.5177 (4)	0.68310 (10)	0.30716 (16)	0.0420 (4)
S1	0.36264 (11)	0.70384 (3)	0.20026 (5)	0.02965 (18)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0313 (12)	0.0354 (12)	0.0275 (10)	−0.0014 (9)	−0.0052 (9)	−0.0003 (9)
C2	0.0292 (11)	0.0281 (10)	0.0270 (10)	−0.0019 (8)	−0.0027 (9)	−0.0010 (8)
C3	0.0292 (11)	0.0307 (11)	0.0298 (10)	−0.0012 (9)	−0.0056 (9)	−0.0011 (9)
C4	0.0343 (13)	0.0323 (11)	0.0340 (11)	−0.0041 (9)	0.0002 (10)	−0.0039 (9)
C5	0.0465 (15)	0.0295 (11)	0.0402 (13)	−0.0049 (10)	−0.0025 (11)	0.0017 (9)
C6	0.0461 (15)	0.0348 (12)	0.0358 (12)	−0.0008 (10)	−0.0079 (11)	0.0054 (10)
C7	0.0363 (13)	0.0409 (13)	0.0264 (11)	−0.0014 (10)	−0.0080 (10)	0.0021 (9)
C8	0.0381 (14)	0.0344 (12)	0.0426 (13)	−0.0063 (10)	−0.0053 (11)	−0.0041 (10)
C9	0.0411 (14)	0.0387 (13)	0.0500 (15)	0.0002 (11)	−0.0014 (12)	−0.0120 (11)
F1	0.0520 (11)	0.0479 (10)	0.0892 (14)	0.0019 (8)	−0.0329 (10)	−0.0072 (9)
F2	0.0700 (14)	0.1067 (17)	0.0459 (10)	−0.0298 (12)	0.0039 (9)	−0.0328 (10)
F3	0.0673 (12)	0.0446 (9)	0.0773 (12)	−0.0257 (8)	−0.0208 (10)	0.0066 (9)
O1	0.0628 (14)	0.0392 (10)	0.0453 (10)	−0.0044 (9)	−0.0255 (10)	−0.0005 (8)
O2	0.0596 (14)	0.0481 (12)	0.0622 (13)	0.0101 (10)	−0.0377 (11)	−0.0121 (10)
O3	0.0279 (9)	0.0490 (10)	0.0441 (10)	−0.0075 (7)	−0.0047 (8)	0.0036 (8)
O4	0.0404 (10)	0.0411 (10)	0.0410 (10)	−0.0038 (7)	−0.0135 (8)	0.0091 (7)
S1	0.0264 (3)	0.0294 (3)	0.0313 (3)	−0.0036 (2)	−0.0070 (2)	0.0017 (2)

Geometric parameters (Å, º) top

C1—C6	1.392 (3)	C7—O1	1.194 (3)
C1—C2	1.410 (3)	C7—O2	1.326 (3)
C1—C7	1.502 (3)	C8—F1	1.322 (3)
C2—C3	1.387 (3)	C8—F3	1.325 (3)
C2—S1	1.796 (2)	C8—F2	1.326 (3)
C3—C4	1.396 (3)	C9—S1	1.753 (3)
C3—H3	0.9300	C9—H9A	0.9600
C4—C5	1.383 (3)	C9—H9B	0.9600
C4—C8	1.498 (3)	C9—H9C	0.9600
C5—C6	1.387 (4)	O2—H2	0.816 (10)
C5—H5	0.9300	O3—S1	1.4325 (18)
C6—H6	0.9300	O4—S1	1.4484 (18)

C6—C1—C2	118.2 (2)	O2—C7—C1	112.0 (2)
C6—C1—C7	118.1 (2)	F1—C8—F3	106.1 (2)
C2—C1—C7	123.6 (2)	F1—C8—F2	107.8 (2)
C3—C2—C1	120.5 (2)	F3—C8—F2	106.0 (2)
C3—C2—S1	114.94 (17)	F1—C8—C4	112.9 (2)
C1—C2—S1	124.32 (17)	F3—C8—C4	112.8 (2)
C2—C3—C4	119.8 (2)	F2—C8—C4	110.8 (2)
C2—C3—H3	120.1	S1—C9—H9A	109.5
C4—C3—H3	120.1	S1—C9—H9B	109.5
C5—C4—C3	120.3 (2)	H9A—C9—H9B	109.5
C5—C4—C8	120.2 (2)	S1—C9—H9C	109.5
C3—C4—C8	119.3 (2)	H9A—C9—H9C	109.5
C4—C5—C6	119.6 (2)	H9B—C9—H9C	109.5
C4—C5—H5	120.2	C7—O2—H2	107 (3)
C6—C5—H5	120.2	O3—S1—O4	116.25 (11)
C5—C6—C1	121.5 (2)	O3—S1—C9	112.01 (13)
C5—C6—H6	119.3	O4—S1—C9	107.14 (13)
C1—C6—H6	119.3	O3—S1—C2	108.76 (11)
O1—C7—O2	122.8 (2)	O4—S1—C2	106.40 (11)
O1—C7—C1	125.2 (2)	C9—S1—C2	105.64 (12)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O4ⁱ	0.82 (1)	1.92 (1)	2.725 (3)	169 (4)
C9—H9B···O3ⁱⁱ	0.96	2.35	3.208 (3)	148

Symmetry codes: (i) x−1, −y+3/2, z−1/2; (ii) x+1, y, z.

Experimental details

Crystal data
Chemical formula	C₉H₇F₃O₄S
M_r	268.21
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	5.0804 (10), 17.345 (4), 11.576 (2)
β (°)	95.41 (3)
V (Å³)	1015.6 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.36
Crystal size (mm)	0.39 × 0.32 × 0.22

Data collection
Diffractometer	Rigaku R-AXIS RAPID diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.871, 0.926
No. of measured, independent and observed [I > 2σ(I)] reflections	9132, 2250, 1879
R_int	0.029
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.044, 0.123, 1.11
No. of reflections	2250
No. of parameters	158
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.39, −0.38

Computer programs: RAPID-AUTO (Rigaku, 1998), CrystalClear (Rigaku/MSC, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O4ⁱ	0.816 (10)	1.920 (13)	2.725 (3)	169 (4)
C9—H9B···O3ⁱⁱ	0.96	2.35	3.208 (3)	148.3

Symmetry codes: (i) x−1, −y+3/2, z−1/2; (ii) x+1, y, z.

Acknowledgements

The authors thank the Project of Innovation Service Platform of Heilongjiang Province (grant No. PG09J001) and Heilongjiang University for support.

References

Cain, P. A., Cramp, S. M., Lambert, C., Wallis, D. I., Yarwood, T. D., Little, G. M., Morris, J., Musil, T., Pettit, S. N. & Smith, P. H. G. (1998). US Patent No. 5804532. Google Scholar
Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan. Google Scholar
Rigaku (1998). RAPID-AUTO. Rigaku Corporation, Tokyo, Japan. Google Scholar
Rigaku/MSC (2002). CrystalClear. Rigaku/MSC Inc., The Woodlands, Texas, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar