Methyl 4-chloro-3,5-dinitro­benzoate

Liu, Y.-L.; Zou, P.; Xie, M.-H.; Wu, H.; He, Y.-J.

doi:10.1107/S1600536809051630

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 66| Part 1| January 2010| Page o62

doi:10.1107/S1600536809051630

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Methyl 4-chloro-3,5-dinitrobenzoate

Ya-Ling Liu,^a ^* Pei Zou,^a Min-Hao Xie,^a Hao Wu ^a and Yong-Jun He ^a

^aJiangsu Institute of Nuclear Medicine, Wuxi 214063, People's Republic of China
^*Correspondence e-mail: liuyaling158@163.com

(Received 26 November 2009; accepted 1 December 2009; online 4 December 2009)

In the molecule of the title compound, C₈H₅ClN₂O₆, the two nitro groups and the ester group make dihedral angles of 29.6 (1)°, 82.3 (1)° and 13.7 (1)°, respectively, with the benzene ring. In the crystal structure weak C—H⋯O interactions are present.

Related literature

For the use of the title compound as a herbicide, see: Akira et al. (1978 ); Ferenc et al. (1984 ).

Experimental

Crystal data

C₈H₅ClN₂O₆
M_r = 260.59
Triclinic, $[P \overline 1]$
a = 4.8579 (10) Å
b = 9.4438 (19) Å
c = 11.369 (2) Å
α = 73.36 (3)°
β = 88.09 (3)°
γ = 87.47 (3)°
V = 499.14 (18) Å³
Z = 2
Mo Kα radiation
μ = 0.40 mm⁻¹
T = 93 K
0.50 × 0.33 × 0.17 mm

Data collection

Rigaku SPIDER diffractometer
Absorption correction: multi-scan (North et al., 1968 ) T_min = 0.824, T_max = 0.936
3935 measured reflections
2193 independent reflections
1607 reflections with I > 2σ(I)
R_int = 0.029
Standard reflections: 0

Refinement

R[F² > 2σ(F²)] = 0.047
wR(F²) = 0.142
S = 1.02
2193 reflections
155 parameters
H-atom parameters constrained
Δρ_max = 0.85 e Å⁻³
Δρ_min = −0.32 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1⋯O1ⁱ	0.95	2.51	3.329 (3)	145
C5—H5⋯O6ⁱⁱ	0.95	2.34	3.143 (3)	142
Symmetry codes: (i) -x+2, -y+1, -z+1; (ii) -x+1, -y+2, -z.

Data collection: RAPID-AUTO (Rigaku 2004 ); cell refinement: RAPID-AUTO; data reduction: RAPID-AUTO; 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 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809051630/xu2697sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809051630/xu2697Isup2.hkl

checkCIF report

Comment top

The title compound (Fig.1) is useful as a herbicide (Akira et al.,1978; Ferenc et al., 1984). It give good result as seed-dressing fungicide for sunflower, corn and flax. We report here the crystal structure of the title compound. Two nitro groups (O1/N1/O2 and O3/N2/O4) attached at C2 and C4, the ester group(O5/C7/O6) attached at C6 form dihedral angles of 150.4 (1)°, 97.7 (1)° and 166.3 (1)° with the mean plane of the C1-benzene ring, respectively. In the crystal structure, adjacent molecules are linked through weak C—H···O hydrogen interactions (Table 1).

Related literature top

For the use of the title compound as a herbicide, see: Akira et al. (1978); Ferenc et al. (1984).

Experimental top

A sample of commercial methyl 4-chloro-3,5-dinitrobenzoate (Aldrich) was crystalized by slow evaporation of a solution in methanol: colourless chunk-shaped crystals were formed after several days.

Computing details top

Data collection: RAPID-AUTO (Rigaku 2004); cell refinement: RAPID-AUTO (Rigaku 2004); data reduction: RAPID-AUTO (Rigaku 2004); 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); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1. A view of the title compound with the atomic numbering scheme. Displacement ellipsoids were drawn at the 30% probability level.

methyl 4-chloro-3,5-dinitrobenzoate top

Crystal data top

C₈H₅ClN₂O₆	Z = 2
M_r = 260.59	F(000) = 264
Triclinic, P1	D_x = 1.734 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 4.8579 (10) Å	Cell parameters from 1306 reflections
b = 9.4438 (19) Å	θ = 3.7–27.5°
c = 11.369 (2) Å	µ = 0.40 mm⁻¹
α = 73.36 (3)°	T = 93 K
β = 88.09 (3)°	Chunk, colorless
γ = 87.47 (3)°	0.50 × 0.33 × 0.17 mm
V = 499.14 (18) Å³

Data collection top

Rigaku SPIDER diffractometer	2193 independent reflections
Radiation source: Rotating Anode	1607 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.029
ω scans	θ_max = 27.5°, θ_min = 3.3°
Absorption correction: multi-scan (North et al., 1968)	h = −6→6
T_min = 0.824, T_max = 0.936	k = −9→12
3935 measured reflections	l = −13→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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.142	H-atom parameters constrained
S = 1.02	w = 1/[σ²(F_o²) + (0.0772P)²] where P = (F_o² + 2F_c²)/3
2193 reflections	(Δ/σ)_max = 0.001
155 parameters	Δρ_max = 0.85 e Å⁻³
0 restraints	Δρ_min = −0.32 e Å⁻³

Crystal data top

C₈H₅ClN₂O₆	γ = 87.47 (3)°
M_r = 260.59	V = 499.14 (18) Å³
Triclinic, P1	Z = 2
a = 4.8579 (10) Å	Mo Kα radiation
b = 9.4438 (19) Å	µ = 0.40 mm⁻¹
c = 11.369 (2) Å	T = 93 K
α = 73.36 (3)°	0.50 × 0.33 × 0.17 mm
β = 88.09 (3)°

Data collection top

Rigaku SPIDER diffractometer	2193 independent reflections
Absorption correction: multi-scan (North et al., 1968)	1607 reflections with I > 2σ(I)
T_min = 0.824, T_max = 0.936	R_int = 0.029
3935 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.047	0 restraints
wR(F²) = 0.142	H-atom parameters constrained
S = 1.02	Δρ_max = 0.85 e Å⁻³
2193 reflections	Δρ_min = −0.32 e Å⁻³
155 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
Cl1	1.27729 (13)	1.05900 (7)	0.37558 (6)	0.0216 (2)
O1	0.9997 (5)	0.6244 (2)	0.56066 (17)	0.0317 (5)
O2	1.3643 (4)	0.7546 (2)	0.51374 (19)	0.0345 (5)
O3	1.1854 (4)	1.2028 (2)	0.07808 (17)	0.0249 (5)
O4	0.8170 (4)	1.2738 (2)	0.16400 (18)	0.0278 (5)
O5	0.4877 (4)	0.58546 (19)	0.21655 (17)	0.0220 (4)
O6	0.3199 (4)	0.79731 (19)	0.08858 (15)	0.0194 (4)
N1	1.1375 (5)	0.7234 (2)	0.4913 (2)	0.0222 (5)
N2	0.9797 (5)	1.1792 (2)	0.1458 (2)	0.0191 (5)
C1	0.8221 (5)	0.7323 (3)	0.3272 (2)	0.0172 (5)
H1	0.7881	0.6315	0.3672	0.021*
C2	1.0070 (5)	0.8080 (3)	0.3755 (2)	0.0175 (5)
C3	1.0622 (5)	0.9551 (3)	0.3184 (2)	0.0164 (5)
C4	0.9246 (5)	1.0237 (3)	0.2102 (2)	0.0172 (5)
C5	0.7370 (5)	0.9523 (3)	0.1612 (2)	0.0171 (5)
H5	0.6432	1.0033	0.0884	0.021*
C6	0.6874 (5)	0.8061 (3)	0.2193 (2)	0.0168 (5)
C7	0.4771 (5)	0.7304 (3)	0.1662 (2)	0.0168 (5)
C8	0.2922 (6)	0.5029 (3)	0.1694 (3)	0.0244 (6)
H8A	0.1036	0.5346	0.1860	0.037*
H8B	0.3196	0.3969	0.2100	0.037*
H8C	0.3221	0.5219	0.0807	0.037*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0217 (4)	0.0228 (4)	0.0222 (4)	−0.0051 (3)	−0.0061 (3)	−0.0083 (3)
O1	0.0396 (13)	0.0269 (11)	0.0254 (11)	−0.0063 (9)	−0.0043 (9)	−0.0013 (9)
O2	0.0279 (12)	0.0400 (13)	0.0325 (12)	−0.0039 (10)	−0.0142 (10)	−0.0035 (10)
O3	0.0229 (10)	0.0239 (10)	0.0253 (10)	−0.0084 (8)	0.0037 (8)	−0.0025 (8)
O4	0.0286 (11)	0.0177 (10)	0.0380 (12)	0.0006 (8)	−0.0006 (9)	−0.0093 (9)
O5	0.0251 (10)	0.0143 (9)	0.0260 (10)	−0.0062 (7)	−0.0078 (8)	−0.0035 (8)
O6	0.0213 (10)	0.0192 (9)	0.0165 (9)	−0.0052 (7)	−0.0055 (8)	−0.0017 (8)
N1	0.0279 (13)	0.0192 (12)	0.0189 (12)	−0.0012 (10)	−0.0085 (10)	−0.0037 (10)
N2	0.0213 (12)	0.0165 (11)	0.0196 (11)	−0.0053 (9)	−0.0058 (9)	−0.0042 (9)
C1	0.0209 (13)	0.0150 (12)	0.0145 (13)	−0.0007 (10)	−0.0014 (10)	−0.0020 (10)
C2	0.0191 (13)	0.0188 (13)	0.0148 (13)	0.0025 (10)	−0.0032 (10)	−0.0053 (10)
C3	0.0145 (12)	0.0191 (13)	0.0174 (13)	−0.0022 (10)	−0.0033 (10)	−0.0074 (11)
C4	0.0173 (13)	0.0136 (12)	0.0192 (13)	−0.0030 (10)	0.0014 (10)	−0.0022 (10)
C5	0.0159 (12)	0.0168 (12)	0.0179 (13)	−0.0018 (10)	−0.0025 (10)	−0.0035 (10)
C6	0.0167 (12)	0.0152 (12)	0.0177 (13)	−0.0015 (10)	−0.0013 (10)	−0.0034 (10)
C7	0.0166 (12)	0.0152 (12)	0.0167 (13)	−0.0039 (10)	0.0009 (11)	−0.0012 (10)
C8	0.0252 (15)	0.0154 (13)	0.0345 (16)	−0.0085 (11)	−0.0045 (12)	−0.0082 (12)

Geometric parameters (Å, º) top

Cl1—C3	1.725 (3)	C1—C6	1.393 (4)
O1—N1	1.242 (3)	C1—H1	0.9500
O2—N1	1.207 (3)	C2—C3	1.388 (4)
O3—N2	1.229 (3)	C3—C4	1.393 (4)
O4—N2	1.224 (3)	C4—C5	1.377 (3)
O5—C7	1.323 (3)	C5—C6	1.378 (3)
O5—C8	1.461 (3)	C5—H5	0.9500
O6—C7	1.202 (3)	C6—C7	1.507 (3)
N1—C2	1.477 (3)	C8—H8A	0.9800
N2—C4	1.473 (3)	C8—H8B	0.9800
C1—C2	1.390 (3)	C8—H8C	0.9800

C7—O5—C8	115.43 (19)	C5—C4—N2	118.5 (2)
O2—N1—O1	124.3 (2)	C3—C4—N2	118.8 (2)
O2—N1—C2	119.4 (2)	C4—C5—C6	119.1 (2)
O1—N1—C2	116.3 (2)	C4—C5—H5	120.4
O4—N2—O3	125.6 (2)	C6—C5—H5	120.4
O4—N2—C4	117.4 (2)	C5—C6—C1	120.3 (2)
O3—N2—C4	117.0 (2)	C5—C6—C7	118.5 (2)
C2—C1—C6	119.2 (2)	C1—C6—C7	121.1 (2)
C2—C1—H1	120.4	O6—C7—O5	125.7 (2)
C6—C1—H1	120.4	O6—C7—C6	122.5 (2)
C3—C2—C1	121.6 (2)	O5—C7—C6	111.8 (2)
C3—C2—N1	122.3 (2)	O5—C8—H8A	109.5
C1—C2—N1	116.1 (2)	O5—C8—H8B	109.5
C2—C3—C4	117.0 (2)	H8A—C8—H8B	109.5
C2—C3—Cl1	124.5 (2)	O5—C8—H8C	109.5
C4—C3—Cl1	118.43 (19)	H8A—C8—H8C	109.5
C5—C4—C3	122.7 (2)	H8B—C8—H8C	109.5

C6—C1—C2—C3	−0.5 (4)	O3—N2—C4—C5	−98.0 (3)
C6—C1—C2—N1	178.8 (2)	O4—N2—C4—C3	−97.7 (3)
O2—N1—C2—C3	−29.5 (4)	O3—N2—C4—C3	82.5 (3)
O1—N1—C2—C3	149.4 (3)	C3—C4—C5—C6	−1.7 (4)
O2—N1—C2—C1	151.2 (3)	N2—C4—C5—C6	178.8 (2)
O1—N1—C2—C1	−29.9 (3)	C4—C5—C6—C1	1.0 (4)
C1—C2—C3—C4	−0.1 (4)	C4—C5—C6—C7	178.7 (2)
N1—C2—C3—C4	−179.4 (2)	C2—C1—C6—C5	0.1 (4)
C1—C2—C3—Cl1	177.2 (2)	C2—C1—C6—C7	−177.6 (2)
N1—C2—C3—Cl1	−2.1 (4)	C8—O5—C7—O6	1.4 (4)
C2—C3—C4—C5	1.3 (4)	C8—O5—C7—C6	−179.4 (2)
Cl1—C3—C4—C5	−176.2 (2)	C5—C6—C7—O6	−12.6 (4)
C2—C3—C4—N2	−179.3 (2)	C1—C6—C7—O6	165.0 (2)
Cl1—C3—C4—N2	3.2 (3)	C5—C6—C7—O5	168.2 (2)
O4—N2—C4—C5	81.8 (3)	C1—C6—C7—O5	−14.2 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···O1ⁱ	0.95	2.51	3.329 (3)	145
C5—H5···O6ⁱⁱ	0.95	2.34	3.143 (3)	142

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

Experimental details

Crystal data
Chemical formula	C₈H₅ClN₂O₆
M_r	260.59
Crystal system, space group	Triclinic, P1
Temperature (K)	93
a, b, c (Å)	4.8579 (10), 9.4438 (19), 11.369 (2)
α, β, γ (°)	73.36 (3), 88.09 (3), 87.47 (3)
V (Å³)	499.14 (18)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.40
Crystal size (mm)	0.50 × 0.33 × 0.17

Data collection
Diffractometer	Rigaku SPIDER diffractometer
Absorption correction	Multi-scan (North et al., 1968)
T_min, T_max	0.824, 0.936
No. of measured, independent and observed [I > 2σ(I)] reflections	3935, 2193, 1607
R_int	0.029
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.047, 0.142, 1.02
No. of reflections	2193
No. of parameters	155
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.85, −0.32

Computer programs: RAPID-AUTO (Rigaku 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···O1ⁱ	0.95	2.5100	3.329 (3)	145
C5—H5···O6ⁱⁱ	0.95	2.3400	3.143 (3)	142

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

Acknowledgements

The authors acknowledge financial support from Jiangsu Institute of Nuclear Medicine, China.

References

Akira, S., Shoji, K. & Kenichi, S. (1978). Japan Patent No. 53101528 Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Ferenc, B., Gyoery, K. & Mihaly, N. (1984). German Patent No. 3410566 Google Scholar
North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359. CrossRef IUCr Journals Web of Science Google Scholar
Rigaku (2004). RAPID-AUTO. Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar