Ethyl 4-chloro-3-nitro­benzoate

Abstract

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,

• a = 12.930 (3) Å

• b = 7.4820 (15) Å

• c = 20.945 (4) Å

• β = 92.11 (3)°

• V = 2024.9 (7) ų

• 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[F ² > 2σ(F ²)] = 0.045

• wR(F ²) = 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

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.

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

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) .

supplementary crystallographic information

Comment

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.

Experimental

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.

Refinement

H atoms were positioned geometrically, with C—H = 0.93, 0.97 and 0.96 Å for aromatic, methylene and methyl H, respectively, and constrained to ride on their parent atoms, with U_iso(H) = xU_eq(C), where x = 1.5 for methyl H, and x = 1.2 for all other H atoms.

Figures

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.

Crystal data

C9H8ClNO4	F000 = 944
Mr = 229.61	Dx = 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 = 9–14º
b = 7.4820 (15) Å	µ = 0.37 mm−1
c = 20.945 (4) Å	T = 298 (2) K
β = 92.11 (3)º	Block, colorless
V = 2024.9 (7) Å3	0.40 × 0.30 × 0.10 mm
Z = 8

Data collection

Enraf–Nonius CAD-4 diffractometer	Rint = 0.0000
Radiation source: fine-focus sealed tube	θmax = 26.0º
Monochromator: graphite	θmin = 2.0º
T = 298(2) K	h = −15→15
ω/2θ scans	k = 0→9
Absorption correction: ψ scan(North et al., 1968)	l = 0→25
Tmin = 0.866, Tmax = 0.964	3 standard reflections
1984 measured reflections	every 120 min
1984 independent reflections	intensity decay: none
1449 reflections with I > 2σ(I)

Refinement

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.045	H-atom parameters constrained
wR(F2) = 0.130	w = 1/[σ2(Fo2) + (0.06P)2 + 1.5P] where P = (Fo2 + 2Fc2)/3
S = 1.06	(Δ/σ)max < 0.001
1984 reflections	Δρmax = 0.16 e Å−3
136 parameters	Δρmin = −0.21 e Å−3
Primary atom site location: structure-invariant direct methods	Extinction correction: none

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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, °)

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, °)

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