Ethyl 4-chloro-3-nitro­benzoate

Li, H.-Y.; Liu, B.-N.; Tang, S.-G.; Xu, Y.-M.; Guo, C.

doi:10.1107/S1600536807068304

organic compounds

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ISSN: 2056-9890

Volume 64| Part 2| February 2008| Page o523

doi:10.1107/S1600536807068304

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Ethyl 4-chloro-3-nitrobenzoate

Hao-Yuan Li,^a Bo-Nian Liu,^a Shi-Gui Tang,^b Ye-Ming Xu ^a and Cheng Guo ^a ^*

^aCollege of Science, Nanjing University of Technology, Xinmofan Road No. 5 Nanjing, Nanjing 210009, People's Republic of China, and ^bCollege of Life Sciences and Pharmaceutical Engineering, Nanjing University of Technology, Nanjing 210009, People's Republic of China
^*Correspondence e-mail: guocheng@njut.edu.cn

(Received 28 November 2007; accepted 24 December 2007; online 25 January 2008)

In the molecule of the title compound, C₉H₈ClNO₄, an intramolecular C—H⋯O hydrogen bond results in the formation of a planar five-membered ring, which is nearly coplanar with the adjacent six-membered ring, the rings being oriented at a dihedral angle of 4.40 (3)°. In the crystal structure, intermolecular C—H⋯O hydrogen bonds link the molecules.

Related literature

For related literature, see: Jönsson et al. (2004 ). For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₉H₈ClNO₄
M_r = 229.61
Monoclinic, C 2/c
a = 12.930 (3) Å
b = 7.4820 (15) Å
c = 20.945 (4) Å
β = 92.11 (3)°
V = 2024.9 (7) Å³
Z = 8
Mo Kα radiation
μ = 0.37 mm⁻¹
T = 298 (2) K
0.40 × 0.30 × 0.10 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.866, T_max = 0.964
1984 measured reflections
1984 independent reflections
1449 reflections with I > 2σ(I)
3 standard reflections frequency: 120 min intensity decay: none

Refinement

R[F² > 2σ(F²)] = 0.045
wR(F²) = 0.130
S = 1.06
1984 reflections
136 parameters
H-atom parameters constrained
Δρ_max = 0.16 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2B⋯O2	0.97	2.29	2.706 (3)	104
C8—H8A⋯O2ⁱ	0.93	2.53	3.357 (3)	148
Symmetry code: (i) $[x+{\script{1\over 2}}, y+{\script{1\over 2}}, z]$ .

Data collection: CAD-4 Software (Enraf–Nonius, 1989 ); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo, 1995 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Siemens, 1996 ); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536807068304/hk2403sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536807068304/hk2403Isup2.hkl

checkCIF report

Comment top

Some derivatives of benzoic acid are important chemical materials. As part of our ongoing studies, we synthesized the title compound, (I), and report herein its crystal structure.

In the molecule of (I), (Fig. 1) the bond lengths and angles are within normal ranges (Allen et al., 1987). The intramolecular C—H···O hydrogen bond (Table 1) results in the formation of a planar five-membered ring B (C2/H2B/C3/O1/O2). Ring A (C4—C9) is, of course, planar and the dihedral angle between them is A/B = 4.40 (3)°. So, rings A and B are also nearly co-planar.

In the crystal structure, intermolecular C—H···O hydrogen bonds (Table 1) link the molecules (Fig. 2), in which they may be effective in the stabilization of the structure.

Related literature top

For related literature, see: Daniel et al. (2004). For bond-length data, see: Allen et al. (1987).

Experimental top

For the preparation of the title compound, 4-chloro-3-nitrobenzoic acid (35.0 g, 174 mmol) was suspended in ethanol (150 ml) and cooled to 273 K. Concentrated sulfuric acid (15 ml) was slowly added with stirring, and then the mixture was heated under reflux for 17 h. Upon cooling to room temperature, a precipitate formed, which was collected by filtration and washed with cold ethanol (2 × 50 ml) and hexane (2 × 50 ml) to afford the ethyl ester as a white solid (yield; 29.9 g, 75%) (Daniel et al., 2004). Crystals of (I) suitable for X-ray analysis were obtained by slow evaporation of a methanol solution.

Computing details top

Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell refinement: CAD-4 Software (Enraf–Nonius, 1989); data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Siemens, 1996); software used to prepare material for publication: SHELXTL (Siemens, 1996).

Figures top

	Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. A packing diagram of (I). Hydrogen bonds are shown as dashed lines.

Ethyl 4-chloro-3-nitrobenzoate top

Crystal data top

C₉H₈ClNO₄	F(000) = 944
M_r = 229.61	D_x = 1.506 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 25 reflections
a = 12.930 (3) Å	θ = 9–14°
b = 7.4820 (15) Å	µ = 0.37 mm⁻¹
c = 20.945 (4) Å	T = 298 K
β = 92.11 (3)°	Block, colorless
V = 2024.9 (7) Å³	0.40 × 0.30 × 0.10 mm
Z = 8

Data collection top

Enraf–Nonius CAD-4 diffractometer	1449 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.000
Graphite monochromator	θ_max = 26.0°, θ_min = 2.0°
ω/2θ scans	h = −15→15
Absorption correction: ψ scan (North et al., 1968)	k = 0→9
T_min = 0.866, T_max = 0.964	l = 0→25
1984 measured reflections	3 standard reflections every 120 min
1984 independent reflections	intensity decay: none

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)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.130	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.06P)² + 1.5P] where P = (F_o² + 2F_c²)/3
1984 reflections	(Δ/σ)_max < 0.001
136 parameters	Δρ_max = 0.16 e Å⁻³
0 restraints	Δρ_min = −0.21 e Å⁻³

Crystal data top

C₉H₈ClNO₄	V = 2024.9 (7) Å³
M_r = 229.61	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 12.930 (3) Å	µ = 0.37 mm⁻¹
b = 7.4820 (15) Å	T = 298 K
c = 20.945 (4) Å	0.40 × 0.30 × 0.10 mm
β = 92.11 (3)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	1449 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.000
T_min = 0.866, T_max = 0.964	3 standard reflections every 120 min
1984 measured reflections	intensity decay: none
1984 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.045	0 restraints
wR(F²) = 0.130	H-atom parameters constrained
S = 1.06	Δρ_max = 0.16 e Å⁻³
1984 reflections	Δρ_min = −0.21 e Å⁻³
136 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
Cl	1.15365 (6)	0.38995 (10)	0.39251 (4)	0.0722 (3)
O1	0.91716 (14)	0.1218 (3)	0.65000 (8)	0.0663 (6)
O2	0.78374 (14)	0.0870 (3)	0.58085 (9)	0.0627 (5)
O3	0.9430 (2)	0.3802 (4)	0.33433 (11)	0.1031 (9)
O4	0.87451 (19)	0.1219 (3)	0.35272 (10)	0.0825 (7)
N	0.92750 (19)	0.2507 (4)	0.36829 (10)	0.0628 (6)
C1	0.8393 (3)	0.2219 (5)	0.74482 (16)	0.0967 (12)
H1A	0.7999	0.1862	0.7807	0.145*
H1B	0.8023	0.3127	0.7210	0.145*
H1C	0.9051	0.2681	0.7598	0.145*
C2	0.8556 (3)	0.0672 (5)	0.70361 (13)	0.0801 (10)
H2A	0.8912	−0.0264	0.7277	0.096*
H2B	0.7894	0.0207	0.6879	0.096*
C3	0.87120 (18)	0.1287 (3)	0.59279 (11)	0.0427 (5)
C4	0.94310 (16)	0.1938 (3)	0.54379 (10)	0.0387 (5)
C5	0.90841 (17)	0.1923 (3)	0.48080 (10)	0.0408 (5)
H5A	0.8426	0.1492	0.4700	0.049*
C6	0.97087 (18)	0.2546 (3)	0.43393 (11)	0.0444 (5)
C7	1.06993 (18)	0.3170 (3)	0.44914 (11)	0.0459 (6)
C8	1.10485 (18)	0.3167 (3)	0.51210 (12)	0.0489 (6)
H8A	1.1711	0.3576	0.5229	0.059*
C9	1.04200 (17)	0.2561 (3)	0.55916 (11)	0.0446 (5)
H9A	1.0660	0.2569	0.6016	0.054*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl	0.0766 (5)	0.0632 (5)	0.0794 (5)	0.0006 (4)	0.0387 (4)	0.0099 (4)
O1	0.0616 (11)	0.0952 (15)	0.0424 (10)	−0.0104 (10)	0.0052 (8)	0.0096 (9)
O2	0.0497 (10)	0.0774 (13)	0.0612 (11)	−0.0127 (9)	0.0065 (8)	0.0051 (9)
O3	0.130 (2)	0.116 (2)	0.0628 (13)	−0.0096 (17)	0.0003 (14)	0.0378 (14)
O4	0.1026 (17)	0.0833 (16)	0.0601 (12)	0.0024 (14)	−0.0146 (11)	−0.0164 (11)
N	0.0721 (15)	0.0704 (16)	0.0461 (12)	0.0122 (13)	0.0057 (11)	0.0025 (12)
C1	0.109 (3)	0.109 (3)	0.074 (2)	0.028 (2)	0.037 (2)	0.012 (2)
C2	0.088 (2)	0.107 (3)	0.0461 (15)	−0.011 (2)	0.0176 (14)	0.0144 (16)
C3	0.0456 (13)	0.0368 (12)	0.0455 (13)	0.0046 (10)	0.0015 (10)	−0.0005 (10)
C4	0.0422 (11)	0.0301 (11)	0.0441 (12)	0.0041 (9)	0.0044 (9)	−0.0015 (9)
C5	0.0397 (11)	0.0347 (11)	0.0480 (13)	0.0031 (9)	0.0012 (9)	−0.0023 (10)
C6	0.0526 (13)	0.0385 (12)	0.0424 (12)	0.0085 (10)	0.0053 (10)	0.0005 (10)
C7	0.0517 (13)	0.0340 (12)	0.0531 (14)	0.0057 (10)	0.0157 (11)	0.0025 (10)
C8	0.0412 (12)	0.0402 (13)	0.0657 (16)	−0.0015 (10)	0.0054 (11)	−0.0038 (11)
C9	0.0424 (12)	0.0443 (13)	0.0472 (13)	0.0021 (10)	0.0009 (10)	−0.0032 (10)

Geometric parameters (Å, º) top

Cl—C7	1.724 (2)	C2—H2B	0.9700
O1—C3	1.319 (3)	C3—C4	1.492 (3)
O1—C2	1.459 (3)	C4—C5	1.378 (3)
O2—C3	1.191 (3)	C4—C9	1.388 (3)
N—O3	1.222 (3)	C5—C6	1.375 (3)
N—O4	1.220 (3)	C5—H5A	0.9300
N—C6	1.466 (3)	C6—C7	1.389 (3)
C1—C2	1.463 (5)	C7—C8	1.378 (4)
C1—H1A	0.9600	C8—C9	1.377 (3)
C1—H1B	0.9600	C8—H8A	0.9300
C1—H1C	0.9600	C9—H9A	0.9300
C2—H2A	0.9700

C3—O1—C2	118.0 (2)	C5—C4—C9	119.3 (2)
O4—N—O3	124.9 (3)	C5—C4—C3	117.84 (19)
O4—N—C6	117.3 (2)	C9—C4—C3	122.8 (2)
O3—N—C6	117.7 (3)	C6—C5—C4	120.1 (2)
C2—C1—H1A	109.5	C6—C5—H5A	119.9
C2—C1—H1B	109.5	C4—C5—H5A	119.9
H1A—C1—H1B	109.5	C5—C6—C7	120.7 (2)
C2—C1—H1C	109.5	C5—C6—N	116.6 (2)
H1A—C1—H1C	109.5	C7—C6—N	122.6 (2)
H1B—C1—H1C	109.5	C8—C7—C6	119.1 (2)
O1—C2—C1	109.1 (3)	C8—C7—Cl	117.85 (19)
O1—C2—H2A	109.9	C6—C7—Cl	123.07 (19)
C1—C2—H2A	109.9	C9—C8—C7	120.3 (2)
O1—C2—H2B	109.9	C9—C8—H8A	119.9
C1—C2—H2B	109.9	C7—C8—H8A	119.9
H2A—C2—H2B	108.3	C8—C9—C4	120.5 (2)
O2—C3—O1	125.0 (2)	C8—C9—H9A	119.8
O2—C3—C4	123.5 (2)	C4—C9—H9A	119.8
O1—C3—C4	111.5 (2)

C3—O1—C2—C1	−109.8 (3)	C3—C4—C5—C6	178.6 (2)
C2—O1—C3—O2	−3.0 (4)	C5—C4—C9—C8	0.3 (3)
C2—O1—C3—C4	177.6 (2)	C3—C4—C9—C8	−179.2 (2)
O4—N—C6—C5	−38.6 (3)	C4—C5—C6—C7	1.0 (3)
O3—N—C6—C5	138.0 (3)	C4—C5—C6—N	−179.2 (2)
O4—N—C6—C7	141.2 (3)	C5—C6—C7—C8	−0.3 (3)
O3—N—C6—C7	−42.2 (3)	N—C6—C7—C8	179.8 (2)
O2—C3—C4—C5	−5.1 (3)	C5—C6—C7—Cl	177.82 (17)
O1—C3—C4—C5	174.2 (2)	N—C6—C7—Cl	−2.0 (3)
O2—C3—C4—C9	174.4 (2)	C6—C7—C8—C9	−0.3 (3)
O1—C3—C4—C9	−6.2 (3)	Cl—C7—C8—C9	−178.58 (18)
C9—C4—C5—C6	−1.0 (3)	C7—C8—C9—C4	0.3 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2B···O2	0.97	2.29	2.706 (3)	104
C8—H8A···O2ⁱ	0.93	2.53	3.357 (3)	148

Symmetry code: (i) x+1/2, y+1/2, z.

Experimental details

Crystal data
Chemical formula	C₉H₈ClNO₄
M_r	229.61
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	298
a, b, c (Å)	12.930 (3), 7.4820 (15), 20.945 (4)
β (°)	92.11 (3)
V (Å³)	2024.9 (7)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.37
Crystal size (mm)	0.40 × 0.30 × 0.10

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.866, 0.964
No. of measured, independent and observed [I > 2σ(I)] reflections	1984, 1984, 1449
R_int	0.000
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.130, 1.06
No. of reflections	1984
No. of parameters	136
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.16, −0.21

Computer programs: CAD-4 Software (Enraf–Nonius, 1989), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Siemens, 1996).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2B···O2	0.9700	2.2900	2.706 (3)	104.00
C8—H8A···O2ⁱ	0.93	2.53	3.357 (3)	148.0

Symmetry code: (i) x+1/2, y+1/2, z.

Acknowledgements

The authors thank Dr Shan Liu. Nanjing University of Technology. for useful discussion and the Center of Testing and Analysis, Nanjing University. for support.

References

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. CrossRef Web of Science Google Scholar
Enraf–Nonius (1989). CAD-4 Software. Version 5.0. Enraf–Nonius, Delft, The Netherlands. Google Scholar
Harms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany. Google Scholar
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North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359. CrossRef IUCr Journals Web of Science Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Siemens (1996). SHELXTL. Version 5.06. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA. Google Scholar