Ethyl 4-chloro-3,5-dinitro­benzoate

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

doi:10.1107/S160053681103978X

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 67| Part 11| November 2011| Page o2917

doi:10.1107/S160053681103978X

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Ethyl 4-chloro-3,5-dinitrobenzoate

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

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

(Received 20 September 2011; accepted 28 September 2011; online 12 October 2011)

In the title compound, C₉H₇ClN₂O₆, the nitro groups and the ester group make dihedral angles of 44.0 (1), 89.6 (1) and 164.1 (1)°, respectively, with the benzene ring. In the crystal, molecules are linked through weak C—H⋯O hydrogen-bonding interactions. Molecules are stacked via π–π interactions about inversion centers, with a centroid–centroid distance of 3.671 (2) Å.

Related literature

For applications of the title compound as a herbicide and a related structure, see: Liu et al. (2010 ).

Experimental

Crystal data

C₉H₇ClN₂O₆
M_r = 274.62
Monoclinic, P 2₁ /c
a = 7.744 (2) Å
b = 21.389 (6) Å
c = 7.241 (2) Å
β = 110.504 (4)°
V = 1123.3 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.36 mm⁻¹
T = 133 K
0.30 × 0.20 × 0.10 mm

Data collection

Rigaku SPIDER diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.899, T_max = 0.965
8777 measured reflections
2549 independent reflections
1939 reflections with I > 2σ(I)
R_int = 0.034

Refinement

R[F² > 2σ(F²)] = 0.041
wR(F²) = 0.098
S = 1.00
2549 reflections
164 parameters
H-atom parameters constrained
Δρ_max = 0.51 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
C5—H5⋯O2ⁱ	0.95	2.32	3.157 (3)	147
Symmetry code: (i) -x+1, -y+1, -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: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053681103978X/pv2450sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681103978X/pv2450Isup2.hkl

Supporting information file. DOI: 10.1107/S160053681103978X/pv2450Isup3.cml

checkCIF report

Comment top

The title compound is useful as a herbicide (Liu et al., 2010). In the title molecule (Fig. 1), two nitro groups (O3/N1/O4 and O5/N2/O6) attached at C2 and C4 and the ester group (O1/C7/O2) attached at C6 form dihedral angles of 44.0 (1), 89.6 (1) and 164.1 (1)°, respectively, with the mean plane of the benzene ring (C1–C6). In the cyrstal structure, the molecules are linked through weak C—H···O hydrogen bonding interactions. The molecules are stacked via π-π interactions, about inversion centers with the ring centroid-centroid distance of 3.671 (2) Å.

Related literature top

For applications of the title compound as a herbicide and a related structure, see: Liu et al. (2010).

Experimental top

A sample of commercial ethyl 4-chloro-3,5-dinitrobenzoate (Aldrich) was crystalized by slow evaporation of a solution in methanol yielding colorless chunky crystals 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: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. A view of the title compound with the atomic numbering scheme. Displacement ellipsoids were drawn at the 50% probability level.
	Fig. 2. Part of the packing of the title compound, viewed down the c direction; dashed lines indicate hydrogen bonds.

Ethyl 4-chloro-3,5-dinitrobenzoate top

Crystal data top

C₉H₇ClN₂O₆	F(000) = 560
M_r = 274.62	D_x = 1.624 Mg m⁻³
Monoclinic, P2₁/c	Melting point: 357(2) K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 7.744 (2) Å	Cell parameters from 2718 reflections
b = 21.389 (6) Å	θ = 3.2–27.5°
c = 7.241 (2) Å	µ = 0.36 mm⁻¹
β = 110.504 (4)°	T = 133 K
V = 1123.3 (5) Å³	Block, colorless
Z = 4	0.30 × 0.20 × 0.10 mm

Data collection top

Rigaku SPIDER diffractometer	2549 independent reflections
Radiation source: Rotating Anode	1939 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.034
ω scans	θ_max = 27.5°, θ_min = 3.8°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −8→10
T_min = 0.899, T_max = 0.965	k = −27→27
8777 measured reflections	l = −9→9

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) = 0.098	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.0496P)² + 0.269P] where P = (F_o² + 2F_c²)/3
2549 reflections	(Δ/σ)_max < 0.001
164 parameters	Δρ_max = 0.51 e Å⁻³
0 restraints	Δρ_min = −0.32 e Å⁻³

Crystal data top

C₉H₇ClN₂O₆	V = 1123.3 (5) Å³
M_r = 274.62	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 7.744 (2) Å	µ = 0.36 mm⁻¹
b = 21.389 (6) Å	T = 133 K
c = 7.241 (2) Å	0.30 × 0.20 × 0.10 mm
β = 110.504 (4)°

Data collection top

Rigaku SPIDER diffractometer	2549 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	1939 reflections with I > 2σ(I)
T_min = 0.899, T_max = 0.965	R_int = 0.034
8777 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.041	0 restraints
wR(F²) = 0.098	H-atom parameters constrained
S = 1.00	Δρ_max = 0.51 e Å⁻³
2549 reflections	Δρ_min = −0.32 e Å⁻³
164 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	0.66615 (7)	0.68101 (2)	0.67393 (8)	0.02902 (15)
O1	0.82698 (18)	0.39122 (6)	0.43011 (19)	0.0229 (3)
O2	0.6015 (2)	0.41837 (6)	0.14870 (19)	0.0283 (3)
O3	0.82102 (19)	0.51915 (7)	1.00581 (19)	0.0269 (3)
O4	0.9456 (2)	0.60842 (7)	0.9835 (2)	0.0402 (4)
O5	0.3393 (3)	0.65336 (10)	0.2213 (3)	0.0610 (6)
O6	0.5882 (3)	0.68236 (8)	0.1760 (3)	0.0562 (6)
N1	0.8513 (2)	0.56285 (8)	0.9112 (2)	0.0237 (4)
N2	0.5021 (3)	0.64949 (8)	0.2496 (2)	0.0286 (4)
C1	0.7812 (2)	0.49987 (8)	0.6145 (3)	0.0172 (4)
H1	0.8417	0.4660	0.6966	0.021*
C2	0.7714 (2)	0.55765 (8)	0.6956 (3)	0.0177 (4)
C3	0.6846 (2)	0.60877 (8)	0.5805 (3)	0.0189 (4)
C4	0.6034 (2)	0.59805 (8)	0.3785 (3)	0.0194 (4)
C5	0.6100 (3)	0.54110 (8)	0.2923 (3)	0.0194 (4)
H5	0.5530	0.5357	0.1539	0.023*
C6	0.7015 (2)	0.49173 (8)	0.4111 (3)	0.0166 (4)
C7	0.7039 (2)	0.43024 (8)	0.3140 (3)	0.0178 (4)
C8	0.8358 (3)	0.32869 (8)	0.3507 (3)	0.0232 (4)
H8A	0.9010	0.3303	0.2551	0.028*
H8B	0.7101	0.3121	0.2829	0.028*
C9	0.9385 (3)	0.28811 (10)	0.5225 (3)	0.0317 (5)
H9A	1.0599	0.3064	0.5927	0.048*
H9B	0.9540	0.2463	0.4752	0.048*
H9C	0.8689	0.2851	0.6121	0.048*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0369 (3)	0.0164 (2)	0.0335 (3)	0.0007 (2)	0.0121 (2)	−0.00696 (19)
O1	0.0279 (8)	0.0157 (6)	0.0196 (7)	0.0058 (5)	0.0016 (6)	−0.0021 (5)
O2	0.0401 (9)	0.0187 (7)	0.0173 (7)	0.0037 (6)	−0.0012 (6)	−0.0029 (5)
O3	0.0299 (8)	0.0321 (8)	0.0197 (7)	0.0041 (6)	0.0102 (6)	0.0041 (6)
O4	0.0530 (10)	0.0306 (9)	0.0267 (8)	−0.0122 (7)	0.0010 (7)	−0.0100 (6)
O5	0.0495 (12)	0.0778 (15)	0.0620 (13)	0.0438 (10)	0.0275 (10)	0.0343 (11)
O6	0.0571 (12)	0.0344 (10)	0.0572 (12)	−0.0177 (8)	−0.0049 (9)	0.0259 (9)
N1	0.0249 (9)	0.0255 (9)	0.0190 (8)	0.0027 (7)	0.0058 (7)	−0.0032 (7)
N2	0.0392 (11)	0.0175 (9)	0.0226 (9)	0.0054 (8)	0.0027 (8)	0.0015 (7)
C1	0.0177 (9)	0.0149 (8)	0.0176 (9)	0.0010 (7)	0.0046 (7)	0.0016 (7)
C2	0.0189 (10)	0.0195 (9)	0.0140 (9)	−0.0019 (7)	0.0048 (7)	−0.0009 (7)
C3	0.0194 (10)	0.0146 (9)	0.0233 (9)	−0.0019 (7)	0.0081 (8)	−0.0029 (7)
C4	0.0211 (10)	0.0151 (9)	0.0211 (9)	0.0026 (7)	0.0063 (8)	0.0042 (7)
C5	0.0224 (10)	0.0180 (9)	0.0164 (9)	0.0001 (7)	0.0051 (8)	0.0015 (7)
C6	0.0180 (9)	0.0146 (8)	0.0172 (8)	−0.0006 (7)	0.0062 (7)	−0.0001 (7)
C7	0.0210 (10)	0.0153 (9)	0.0179 (9)	0.0010 (7)	0.0077 (8)	0.0017 (7)
C8	0.0300 (11)	0.0140 (9)	0.0230 (10)	0.0032 (8)	0.0062 (8)	−0.0029 (7)
C9	0.0426 (13)	0.0225 (11)	0.0285 (11)	0.0077 (9)	0.0104 (10)	0.0031 (8)

Geometric parameters (Å, º) top

Cl1—C3	1.7125 (19)	C2—C3	1.396 (3)
O1—C7	1.323 (2)	C3—C4	1.394 (3)
O1—C8	1.467 (2)	C4—C5	1.378 (3)
O2—C7	1.209 (2)	C5—C6	1.389 (2)
O3—N1	1.229 (2)	C5—H5	0.9500
O4—N1	1.220 (2)	C6—C7	1.495 (2)
O5—N2	1.207 (2)	C8—C9	1.497 (3)
O6—N2	1.213 (2)	C8—H8A	0.9900
N1—C2	1.468 (2)	C8—H8B	0.9900
N2—C4	1.478 (2)	C9—H9A	0.9800
C1—C2	1.382 (2)	C9—H9B	0.9800
C1—C6	1.394 (2)	C9—H9C	0.9800
C1—H1	0.9500

C7—O1—C8	116.64 (14)	C4—C5—H5	120.6
O4—N1—O3	124.79 (17)	C6—C5—H5	120.6
O4—N1—C2	118.86 (16)	C5—C6—C1	120.02 (16)
O3—N1—C2	116.32 (16)	C5—C6—C7	117.72 (16)
O5—N2—O6	126.00 (19)	C1—C6—C7	122.22 (16)
O5—N2—C4	116.76 (18)	O2—C7—O1	124.99 (17)
O6—N2—C4	117.18 (18)	O2—C7—C6	122.60 (16)
C2—C1—C6	119.39 (16)	O1—C7—C6	112.40 (15)
C2—C1—H1	120.3	O1—C8—C9	106.70 (16)
C6—C1—H1	120.3	O1—C8—H8A	110.4
C1—C2—C3	122.25 (17)	C9—C8—H8A	110.4
C1—C2—N1	117.00 (16)	O1—C8—H8B	110.4
C3—C2—N1	120.72 (16)	C9—C8—H8B	110.4
C4—C3—C2	116.31 (16)	H8A—C8—H8B	108.6
C4—C3—Cl1	119.57 (14)	C8—C9—H9A	109.5
C2—C3—Cl1	124.07 (15)	C8—C9—H9B	109.5
C5—C4—C3	123.11 (17)	H9A—C9—H9B	109.5
C5—C4—N2	117.89 (17)	C8—C9—H9C	109.5
C3—C4—N2	118.99 (16)	H9A—C9—H9C	109.5
C4—C5—C6	118.89 (17)	H9B—C9—H9C	109.5

C6—C1—C2—C3	−0.3 (3)	O5—N2—C4—C3	−90.7 (2)
C6—C1—C2—N1	177.67 (16)	O6—N2—C4—C3	92.1 (2)
O4—N1—C2—C1	136.26 (18)	C3—C4—C5—C6	0.1 (3)
O3—N1—C2—C1	−41.8 (2)	N2—C4—C5—C6	−178.79 (17)
O4—N1—C2—C3	−45.8 (3)	C4—C5—C6—C1	1.4 (3)
O3—N1—C2—C3	136.14 (17)	C4—C5—C6—C7	179.03 (16)
C1—C2—C3—C4	1.6 (3)	C2—C1—C6—C5	−1.3 (3)
N1—C2—C3—C4	−176.24 (16)	C2—C1—C6—C7	−178.82 (16)
C1—C2—C3—Cl1	179.17 (14)	C8—O1—C7—O2	−1.0 (3)
N1—C2—C3—Cl1	1.3 (3)	C8—O1—C7—C6	177.99 (15)
C2—C3—C4—C5	−1.5 (3)	C5—C6—C7—O2	−15.2 (3)
Cl1—C3—C4—C5	−179.18 (15)	C1—C6—C7—O2	162.35 (18)
C2—C3—C4—N2	177.30 (17)	C5—C6—C7—O1	165.76 (16)
Cl1—C3—C4—N2	−0.4 (2)	C1—C6—C7—O1	−16.6 (2)
O5—N2—C4—C5	88.2 (2)	C7—O1—C8—C9	−163.27 (17)
O6—N2—C4—C5	−89.0 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5···O2ⁱ	0.95	2.32	3.157 (3)	147

Symmetry code: (i) −x+1, −y+1, −z.

Experimental details

Crystal data
Chemical formula	C₉H₇ClN₂O₆
M_r	274.62
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	133
a, b, c (Å)	7.744 (2), 21.389 (6), 7.241 (2)
β (°)	110.504 (4)
V (Å³)	1123.3 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.36
Crystal size (mm)	0.30 × 0.20 × 0.10

Data collection
Diffractometer	Rigaku SPIDER diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.899, 0.965
No. of measured, independent and observed [I > 2σ(I)] reflections	8777, 2549, 1939
R_int	0.034
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.098, 1.00
No. of reflections	2549
No. of parameters	164
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.51, −0.32

Computer programs: RAPID-AUTO (Rigaku, 2004), 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
C5—H5···O2ⁱ	0.95	2.32	3.157 (3)	147

Symmetry code: (i) −x+1, −y+1, −z.

Acknowledgements

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

References

Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan. Google Scholar
Liu, Y.-L., Zou, P., Xie, M.-H., Wu, H. & He, Y.-J. (2010). Acta Cryst. E66, o62. Web of Science CSD CrossRef IUCr Journals 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