Methyl 4-methyl­sulfonyl-2-nitro­benzoate

Hou, Y.-J.; Chu, W.-Y.; Sui, J.; Sun, Z.-Z.

doi:10.1107/S1600536810021914

organic compounds

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ISSN: 2056-9890

Volume 66| Part 7| July 2010| Page o1669

doi:10.1107/S1600536810021914

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Methyl 4-methylsulfonyl-2-nitrobenzoate

Yan-Jun Hou,^a Wen-Yi Chu,^a Jun Sui ^a and Zhi-Zhong Sun ^a ^*

^aCollege of Chemistry and Materials Science, Heilongjiang University, Harbin 150080, People's Republic of China
^*Correspondence e-mail: hljusunzhizhong@163.com

(Received 8 May 2010; accepted 8 June 2010; online 16 June 2010)

The title compound, C₉H₉NO₆S, was prepared by the reaction of methanol and thionyl chloride with 4-methylsulfonyl-2-nitrobenzoic acid under mild conditions. The dihedral angle between the nitro group and benzene ring is 21.33 (19)° and that between the carboxylate group and the benzene ring is 72.09 (17)°. The crystal structure is stabilized by weak intermolecular bifurcated C—H⋯O interactions occurring in the (100) plane.

Related literature

For general background to the synthesis and properties of 4-methylsulfonyl-2-nitro-benzoic acid methyl ester, see: Carter et al. (1991 ). For the biological activity of 4-methylsulfonyl-2-nitro-benzoic acid methyl ester derivatives, see: Kopsell et al. (2009 ).

Experimental

Crystal data

C₉H₉NO₆S
M_r = 259.23
Monoclinic, P 2₁ /c
a = 9.0108 (12) Å
b = 8.7671 (11) Å
c = 14.4761 (19) Å
β = 98.955 (2)°
V = 1129.7 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.30 mm⁻¹
T = 273 K
0.20 × 0.20 × 0.18 mm

Data collection

Bruker SMART APEXII CCD detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.942, T_max = 0.948
9661 measured reflections
2783 independent reflections
2042 reflections with I > 2σ(I)
R_int = 0.028

Refinement

R[F² > 2σ(F²)] = 0.041
wR(F²) = 0.111
S = 1.05
2783 reflections
156 parameters
H-atom parameters constrained
Δρ_max = 0.22 e Å⁻³
Δρ_min = −0.33 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C6—H6⋯O2ⁱ	0.93	2.54	3.370 (2)	148
C6—H6⋯O3ⁱⁱ	0.93	2.59	3.216 (2)	125
Symmetry codes: (i) $[-x, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2004 ); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT; 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: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810021914/kj2147sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810021914/kj2147Isup2.hkl

checkCIF report

Comment top

4-methylsulfonyl-2-nitro-benzoic acid methyl ester is used for preparation of mesotrione, which inhibits a critical enzyme, phytoene desaturase, in plant carotenoidbiosynthesis (Kopsell et al., 2009).

The structure of the title compound is shown in Fig. 1. The dihedral angle between the nitro group and benzene ring is 21.33 (19)°. The dihedral angle between the carboxyl group and benzene ring is 72.09 (17)°. The crystal structure is stabilized by weak intermolecular bifurcated C—H···O interactions (the sum of the angles involving H6 as the central atom is 360 (3)°) occurring in the (100) plane (Table 1), resulting in a two-dimensional network (Fig. 2).

Related literature top

For general background to the synthesis and properties of 4-methylsulfonyl-2-nitro-benzoic acid methyl ester, see: Carter et al. (1991). For the biological activity of 4-methylsulfonyl-2-nitro-benzoic acid methyl ester derivatives, see: Kopsell et al. (2009).

Experimental top

Thionyl chloride (250 mmol) was added to a solution of 4-methylsulfonyl-2-nitro-benzoic acid (50 mmol) in anhydrous toluene (250 ml). After stirring the reaction mixture for 10 h at room temperature, the solvent was removed and methanol (100 ml) was added. The reaction mixture was further stirred for 3 h at 323 K. The resulting oil was washed with water (100 ml). After separation from the water phase, the product was concentrated under reduced pressure and the residue was recrystallized from methanol to give the title compound in a yield of 80% (Carter et al., 1991). Crystals suitable for single-crystal X-ray diffraction were obtained by recrystallization from ethanol at room temperature in a yield of 60%. Analysis found: C 41.7, H 3.4, N 5.3%; C₉H₉NO₆S requires: C 41.7, H 3.5, N 5.4%.

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); 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: publCIF (Westrip, 2010).

Figures top

	Fig. 1. The molecular structure of the title compound, with displacement ellipsoids drawn at the 50% probability level.
	Fig. 2. Part of packing of the crystal structure of the title compound, viewed down the b direction. Dashed lines indicate hydrogen bonds.

Methyl 4-methylsulfonyl-2-nitrobenzoate top

Crystal data top

C₉H₉NO₆S	F(000) = 536
M_r = 259.23	D_x = 1.524 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2311 reflections
a = 9.0108 (12) Å	θ = 2.9–25.0°
b = 8.7671 (11) Å	µ = 0.30 mm⁻¹
c = 14.4761 (19) Å	T = 273 K
β = 98.955 (2)°	Block, colorless
V = 1129.7 (3) Å³	0.20 × 0.20 × 0.18 mm
Z = 4

Data collection top

Bruker SMART APEX CCD detector diffractometer	2783 independent reflections
Radiation source: fine-focus sealed tube	2042 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.028
phi and ω scans	θ_max = 28.3°, θ_min = 2.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −11→11
T_min = 0.942, T_max = 0.948	k = −11→10
9661 measured reflections	l = −19→19

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 = 1.05	w = 1/[σ²(F_o²) + (0.047P)² + 0.3279P] where P = (F_o² + 2F_c²)/3
2783 reflections	(Δ/σ)_max < 0.001
156 parameters	Δρ_max = 0.22 e Å⁻³
0 restraints	Δρ_min = −0.33 e Å⁻³

Crystal data top

C₉H₉NO₆S	V = 1129.7 (3) Å³
M_r = 259.23	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 9.0108 (12) Å	µ = 0.30 mm⁻¹
b = 8.7671 (11) Å	T = 273 K
c = 14.4761 (19) Å	0.20 × 0.20 × 0.18 mm
β = 98.955 (2)°

Data collection top

Bruker SMART APEX CCD detector diffractometer	2783 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2042 reflections with I > 2σ(I)
T_min = 0.942, T_max = 0.948	R_int = 0.028
9661 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.041	0 restraints
wR(F²) = 0.111	H-atom parameters constrained
S = 1.05	Δρ_max = 0.22 e Å⁻³
2783 reflections	Δρ_min = −0.33 e Å⁻³
156 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
S1	−0.24972 (5)	0.42896 (5)	0.03839 (4)	0.04280 (16)
O6	0.42147 (14)	0.11875 (17)	0.20037 (9)	0.0491 (4)
O5	0.28877 (18)	−0.09358 (17)	0.15947 (13)	0.0665 (5)
O4	0.32570 (17)	0.07267 (19)	−0.01616 (11)	0.0608 (4)
O3	0.12224 (18)	0.08499 (19)	−0.11609 (9)	0.0581 (4)
O2	−0.26056 (19)	0.53991 (19)	0.10923 (12)	0.0694 (5)
O1	−0.24582 (17)	0.48263 (19)	−0.05419 (11)	0.0613 (4)
N1	0.19276 (18)	0.10350 (18)	−0.03781 (11)	0.0399 (4)
C1	−0.3960 (2)	0.2976 (3)	0.0338 (2)	0.0737 (8)
H1A	−0.4905	0.3496	0.0188	0.111*
H1B	−0.3909	0.2482	0.0934	0.111*
H1C	−0.3872	0.2227	−0.0134	0.111*
C2	−0.0851 (2)	0.3192 (2)	0.07342 (12)	0.0383 (4)
C4	0.11351 (19)	0.16778 (19)	0.03452 (11)	0.0333 (4)
C3	−0.01499 (19)	0.2509 (2)	0.00566 (12)	0.0361 (4)
H3	−0.0535	0.2607	−0.0575	0.043*
C5	0.1726 (2)	0.1479 (2)	0.12854 (12)	0.0380 (4)
C8	0.3013 (2)	0.0425 (2)	0.16253 (13)	0.0417 (4)
C7	−0.0276 (2)	0.3049 (3)	0.16756 (13)	0.0502 (5)
H7	−0.0750	0.3526	0.2124	0.060*
C6	0.1005 (2)	0.2193 (2)	0.19439 (13)	0.0489 (5)
H6	0.1388	0.2094	0.2576	0.059*
C9	0.5498 (2)	0.0281 (3)	0.24167 (17)	0.0684 (7)
H9A	0.5205	−0.0387	0.2882	0.103*
H9B	0.6285	0.0945	0.2703	0.103*
H9C	0.5853	−0.0313	0.1939	0.103*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0366 (3)	0.0341 (3)	0.0543 (3)	0.00290 (19)	−0.0033 (2)	0.0009 (2)
O6	0.0375 (7)	0.0557 (9)	0.0497 (8)	−0.0009 (6)	−0.0073 (6)	0.0037 (6)
O5	0.0590 (10)	0.0406 (9)	0.0924 (12)	0.0075 (7)	−0.0115 (9)	0.0010 (8)
O4	0.0422 (8)	0.0762 (11)	0.0641 (10)	0.0123 (8)	0.0087 (7)	−0.0088 (8)
O3	0.0607 (9)	0.0771 (11)	0.0362 (8)	0.0002 (8)	0.0061 (7)	−0.0069 (7)
O2	0.0670 (11)	0.0601 (10)	0.0752 (11)	0.0246 (8)	−0.0075 (8)	−0.0210 (8)
O1	0.0565 (10)	0.0612 (10)	0.0608 (9)	0.0055 (8)	−0.0081 (7)	0.0182 (8)
N1	0.0409 (9)	0.0378 (9)	0.0414 (9)	−0.0030 (7)	0.0072 (7)	0.0010 (6)
C1	0.0395 (12)	0.0476 (14)	0.134 (2)	−0.0002 (10)	0.0131 (13)	0.0101 (14)
C2	0.0344 (9)	0.0383 (10)	0.0400 (10)	0.0025 (8)	−0.0006 (7)	0.0024 (7)
C4	0.0332 (9)	0.0318 (9)	0.0341 (9)	−0.0039 (7)	0.0029 (7)	−0.0008 (7)
C3	0.0353 (9)	0.0368 (10)	0.0341 (9)	−0.0032 (7)	−0.0010 (7)	0.0025 (7)
C5	0.0376 (9)	0.0357 (10)	0.0380 (9)	0.0016 (7)	−0.0022 (7)	−0.0004 (7)
C8	0.0387 (10)	0.0458 (12)	0.0383 (10)	0.0032 (8)	−0.0015 (7)	0.0010 (8)
C7	0.0546 (12)	0.0569 (13)	0.0381 (10)	0.0170 (10)	0.0038 (9)	−0.0044 (9)
C6	0.0561 (12)	0.0555 (12)	0.0318 (9)	0.0145 (10)	−0.0037 (8)	−0.0028 (9)
C9	0.0412 (12)	0.0959 (19)	0.0622 (14)	0.0130 (12)	−0.0100 (10)	0.0143 (13)

Geometric parameters (Å, º) top

S1—O1	1.4260 (16)	C2—C3	1.383 (3)
S1—O2	1.4278 (16)	C2—C7	1.386 (2)
S1—C1	1.744 (2)	C4—C3	1.377 (2)
S1—C2	1.7749 (18)	C4—C5	1.393 (2)
O6—C8	1.317 (2)	C3—H3	0.9300
O6—C9	1.453 (2)	C5—C6	1.384 (3)
O5—C8	1.198 (2)	C5—C8	1.504 (3)
O4—N1	1.220 (2)	C7—C6	1.381 (3)
O3—N1	1.221 (2)	C7—H7	0.9300
N1—C4	1.469 (2)	C6—H6	0.9300
C1—H1A	0.9600	C9—H9A	0.9600
C1—H1B	0.9600	C9—H9B	0.9600
C1—H1C	0.9600	C9—H9C	0.9600

O1—S1—O2	117.69 (11)	C4—C3—C2	117.99 (15)
O1—S1—C1	108.11 (12)	C4—C3—H3	121.0
O2—S1—C1	109.99 (13)	C2—C3—H3	121.0
O1—S1—C2	107.80 (9)	C6—C5—C4	117.83 (16)
O2—S1—C2	108.17 (9)	C6—C5—C8	118.24 (16)
C1—S1—C2	104.24 (10)	C4—C5—C8	123.69 (17)
C8—O6—C9	116.36 (18)	O5—C8—O6	125.95 (18)
O4—N1—O3	123.86 (17)	O5—C8—C5	122.42 (17)
O4—N1—C4	117.96 (15)	O6—C8—C5	111.49 (17)
O3—N1—C4	118.18 (15)	C6—C7—C2	119.59 (18)
S1—C1—H1A	109.5	C6—C7—H7	120.2
S1—C1—H1B	109.5	C2—C7—H7	120.2
H1A—C1—H1B	109.5	C7—C6—C5	120.91 (17)
S1—C1—H1C	109.5	C7—C6—H6	119.5
H1A—C1—H1C	109.5	C5—C6—H6	119.5
H1B—C1—H1C	109.5	O6—C9—H9A	109.5
C3—C2—C7	121.07 (17)	O6—C9—H9B	109.5
C3—C2—S1	119.07 (13)	H9A—C9—H9B	109.5
C7—C2—S1	119.85 (15)	O6—C9—H9C	109.5
C3—C4—C5	122.57 (16)	H9A—C9—H9C	109.5
C3—C4—N1	117.78 (15)	H9B—C9—H9C	109.5
C5—C4—N1	119.60 (15)

O1—S1—C2—C3	−25.21 (18)	N1—C4—C5—C6	175.52 (17)
O2—S1—C2—C3	−153.45 (16)	C3—C4—C5—C8	172.23 (17)
C1—S1—C2—C3	89.52 (18)	N1—C4—C5—C8	−10.2 (3)
O1—S1—C2—C7	153.91 (17)	C9—O6—C8—O5	0.2 (3)
O2—S1—C2—C7	25.7 (2)	C9—O6—C8—C5	175.83 (17)
C1—S1—C2—C7	−91.4 (2)	C6—C5—C8—O5	103.2 (2)
O4—N1—C4—C3	157.53 (17)	C4—C5—C8—O5	−71.0 (3)
O3—N1—C4—C3	−22.0 (2)	C6—C5—C8—O6	−72.6 (2)
O4—N1—C4—C5	−20.2 (2)	C4—C5—C8—O6	113.1 (2)
O3—N1—C4—C5	160.31 (17)	C3—C2—C7—C6	−0.9 (3)
C5—C4—C3—C2	1.4 (3)	S1—C2—C7—C6	179.96 (17)
N1—C4—C3—C2	−176.25 (15)	C2—C7—C6—C5	0.2 (3)
C7—C2—C3—C4	0.2 (3)	C4—C5—C6—C7	1.2 (3)
S1—C2—C3—C4	179.26 (13)	C8—C5—C6—C7	−173.4 (2)
C3—C4—C5—C6	−2.1 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6···O2ⁱ	0.93	2.54	3.370 (2)	148
C6—H6···O3ⁱⁱ	0.93	2.59	3.216 (2)	125

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

Experimental details

Crystal data
Chemical formula	C₉H₉NO₆S
M_r	259.23
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	273
a, b, c (Å)	9.0108 (12), 8.7671 (11), 14.4761 (19)
β (°)	98.955 (2)
V (Å³)	1129.7 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.30
Crystal size (mm)	0.20 × 0.20 × 0.18

Data collection
Diffractometer	Bruker SMART APEX CCD detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.942, 0.948
No. of measured, independent and observed [I > 2σ(I)] reflections	9661, 2783, 2042
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.667

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.111, 1.05
No. of reflections	2783
No. of parameters	156
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.22, −0.33

Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6···O2ⁱ	0.93	2.54	3.370 (2)	148.2
C6—H6···O3ⁱⁱ	0.93	2.59	3.216 (2)	125.2

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

Acknowledgements

We thank the National Natural Science Foundation of China (No. 20872030) and Heilongjiang University, China, for supporting this study.

References

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