Methyl 4-chloro-3-nitro­benzoate

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

doi:10.1107/S1600536807067219

organic compounds

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ISSN: 2056-9890

Volume 64| Part 2| February 2008| Page o456

doi:10.1107/S1600536807067219

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Methyl 4-chloro-3-nitrobenzoate

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

^aCollege of Science, Nanjing University of Technology, Xinmofan Road No. 5, 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 19 November 2007; accepted 16 December 2007; online 16 January 2008)

In the title compound, C₈H₆ClNO₄, the molecules are linked by C—H⋯O interactions to form a chain parallel to the a axis. The chains are further connected by slipped π–π stacking between symmetry-related benzene rings, with a centroid-to-centroid distance of 3.646 (2) Å and an interplanar distance of 3.474 Å, resulting in an offset of 1.106 Å.

Related literature

For related literature, see: de Souza et al. (2006 ); Jin & Xiao (2005 ); Spiniello & White (2003 ); Jönssen et al. (2004 ); Andrews & Ladlow (2003 ).

Experimental

Crystal data

C₈H₆ClNO₄
M_r = 215.59
Triclinic, $[P \overline 1]$
a = 7.338 (1) Å
b = 7.480 (1) Å
c = 9.715 (2) Å
α = 98.39 (3)°
β = 94.89 (3)°
γ = 118.95 (3)°
V = 454.1 (2) Å³
Z = 2
Mo Kα radiation
μ = 0.41 mm⁻¹
T = 293 (2) K
0.40 × 0.10 × 0.10 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.854, T_max = 0.961
1918 measured reflections
1773 independent reflections
1389 reflections with I > 2σ(I)
R_int = 0.019
3 standard reflections every 200 reflections intensity decay: none

Refinement

R[F² > 2σ(F²)] = 0.046
wR(F²) = 0.142
S = 1.12
1773 reflections
128 parameters
H-atom parameters constrained
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.24 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C5—H5⋯O2ⁱ	0.93	2.47	3.272 (3)	145
Symmetry code: (i) x+1, y, 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, 1997 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII (Burnett & Johnson, 1996 ), ORTEP-3 for Windows (Farrugia, 1997 ) and PLATON (Spek, 2003 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536807067219/dn2295sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536807067219/dn2295Isup2.hkl

checkCIF report

Comment top

Some derivatives of benzoic acid are important chemical materials. We report here the crystal structure of the title compound, (I).

In compound (I) the nitro group is twisted with respect to the phenyl ring making a dihedral angle of 45.4 (1)° (Fig. 1). Similar twisted conformations are observed in related structures where the aryl ring bears nitro and halide adjacent to each other (de Souza et al., 2006; Spiniello & White, 2003), whereas a planar conformation is observed in other case (Jin & Xiao, 2005).

The molecules of (I) are linked by C—H···O interactions to form a chain parallel to the a axis (Table 1, Fig. 2). The chains are further connected by slippest π–π stacking between symmetry related phenyl rings with a centroit to centroid distance Cg1···Cg1i (Symmetry code: (i) 1 - x, 1 - y, 1 - z) of 3.646 (2) Å and an interplanar distance of 3.474 Å resulting in an offset of 1.106 Å.

Related literature top

For related literature, see: de Souza et al. (2006); Harms & Wocadlo (1995); Jin & Xiao (2005); Spek (2003); Spiniello & White (2003); Jönssen et al. (2004); Andrews & Ladlow (2003).

Experimental top

4-Chloro-3-nitrobenzoic acid (35.0 g, 0.174 mol) was suspended in methanol (150 ml) and cooled to 0°. Concentrated sulfuric acid (15 ml) was slowly added with stirring, and then the mixture was heated at reflux for 17 h. Upon cooling to room temperature, a precipitate formed, which was collected by filtration and washed with cold methanol (2*50 ml) and hexane (2*50 ml) to afford the methyl ester as a white solid (31.8 g, 85%) (Andrews & Ladlow, 2003; Jönssen et al., 2004). Pure compound (I) was obstained by crystallizing from methanol. Crystals of (I) suitable for X-ray diffraction were obstained by slow evaporation of an 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, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII (Burnett & Johnson, 1996), ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).

Figures top

	Fig. 1. The molecular structure of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms are represented as small spheres of arbitrary radii.
	Fig. 2. Partial packing view of (I) showing the formation of the chain through C—H···O hydrogen bonds indicated as dashed lines. H atoms not involved in hydrogen bondings have been omitted for clarity. [Symmetry code: (i) 1 + x, y, z]

Methyl 4-chloro-3-nitrobenzoate top

Crystal data top

C₈H₆ClNO₄	Z = 2
M_r = 215.59	F(000) = 220
Triclinic, P1	D_x = 1.577 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.338 (1) Å	Cell parameters from 25 reflections
b = 7.480 (1) Å	θ = 9–13°
c = 9.715 (2) Å	µ = 0.41 mm⁻¹
α = 98.39 (3)°	T = 293 K
β = 94.89 (3)°	Box, colourless
γ = 118.95 (3)°	0.40 × 0.10 × 0.10 mm
V = 454.1 (2) Å³

Data collection top

Enraf–Nonius CAD-4 diffractometer	1389 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.019
Graphite monochromator	θ_max = 26.0°, θ_min = 2.2°
ω/2θ scans	h = 0→9
Absorption correction: ψ scan (North et al., 1968)	k = −9→8
T_min = 0.854, T_max = 0.961	l = −11→11
1918 measured reflections	3 standard reflections every 200 reflections
1773 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)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.142	H-atom parameters constrained
S = 1.12	w = 1/[σ²(F_o²) + (0.0588P)² + 0.2181P] where P = (F_o² + 2F_c²)/3
1773 reflections	(Δ/σ)_max = 0.001
128 parameters	Δρ_max = 0.21 e Å⁻³
0 restraints	Δρ_min = −0.24 e Å⁻³

Crystal data top

C₈H₆ClNO₄	γ = 118.95 (3)°
M_r = 215.59	V = 454.1 (2) Å³
Triclinic, P1	Z = 2
a = 7.338 (1) Å	Mo Kα radiation
b = 7.480 (1) Å	µ = 0.41 mm⁻¹
c = 9.715 (2) Å	T = 293 K
α = 98.39 (3)°	0.40 × 0.10 × 0.10 mm
β = 94.89 (3)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	1389 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.019
T_min = 0.854, T_max = 0.961	3 standard reflections every 200 reflections
1918 measured reflections	intensity decay: none
1773 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.046	0 restraints
wR(F²) = 0.142	H-atom parameters constrained
S = 1.12	Δρ_max = 0.21 e Å⁻³
1773 reflections	Δρ_min = −0.24 e Å⁻³
128 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
C1	−0.2034 (5)	0.0805 (6)	0.0613 (3)	0.0722 (9)
H1A	−0.3435	−0.0080	0.0779	0.108*
H1B	−0.1832	0.0171	−0.0248	0.108*
H1C	−0.1857	0.2143	0.0536	0.108*
C2	−0.0585 (4)	0.1907 (4)	0.3056 (3)	0.0454 (6)
C3	0.1131 (4)	0.2225 (4)	0.4166 (3)	0.0417 (6)
C4	0.2701 (4)	0.1747 (4)	0.3866 (3)	0.0502 (7)
H4	0.2672	0.1180	0.2941	0.060*
C5	0.4285 (4)	0.2108 (4)	0.4925 (3)	0.0536 (7)
H5	0.5306	0.1769	0.4709	0.064*
C6	0.4376 (4)	0.2965 (4)	0.6299 (3)	0.0497 (6)
C7	0.2808 (4)	0.3452 (4)	0.6588 (3)	0.0459 (6)
C8	0.1197 (4)	0.3055 (4)	0.5547 (3)	0.0425 (6)
H8	0.0146	0.3344	0.5771	0.051*
Cl	0.63808 (12)	0.33572 (14)	0.75859 (9)	0.0731 (3)
N1	0.2849 (4)	0.4450 (4)	0.8022 (2)	0.0569 (6)
O1	−0.0490 (3)	0.1079 (3)	0.1782 (2)	0.0591 (5)
O2	−0.1910 (3)	0.2373 (3)	0.3279 (2)	0.0626 (6)
O3	0.4525 (4)	0.5930 (4)	0.8665 (2)	0.0838 (7)
O4	0.1169 (4)	0.3786 (4)	0.8445 (2)	0.0801 (7)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.075 (2)	0.089 (2)	0.0466 (17)	0.0412 (19)	0.0021 (15)	0.0024 (15)
C2	0.0449 (14)	0.0383 (13)	0.0488 (15)	0.0175 (11)	0.0148 (11)	0.0063 (11)
C3	0.0406 (13)	0.0343 (12)	0.0489 (14)	0.0170 (10)	0.0144 (11)	0.0086 (10)
C4	0.0533 (15)	0.0490 (15)	0.0560 (16)	0.0298 (13)	0.0225 (13)	0.0108 (12)
C5	0.0475 (15)	0.0572 (16)	0.0691 (18)	0.0328 (13)	0.0226 (13)	0.0198 (14)
C6	0.0412 (13)	0.0462 (14)	0.0633 (17)	0.0207 (12)	0.0122 (12)	0.0191 (12)
C7	0.0466 (14)	0.0388 (13)	0.0491 (15)	0.0187 (11)	0.0126 (11)	0.0085 (11)
C8	0.0399 (13)	0.0363 (12)	0.0532 (15)	0.0199 (10)	0.0147 (11)	0.0084 (10)
Cl	0.0564 (5)	0.0836 (6)	0.0821 (6)	0.0363 (4)	0.0021 (4)	0.0278 (4)
N1	0.0682 (16)	0.0606 (15)	0.0451 (13)	0.0349 (13)	0.0112 (12)	0.0106 (11)
O1	0.0626 (12)	0.0725 (13)	0.0444 (10)	0.0400 (11)	0.0080 (9)	−0.0024 (9)
O2	0.0584 (12)	0.0832 (15)	0.0574 (12)	0.0468 (11)	0.0118 (9)	0.0049 (10)
O3	0.0794 (16)	0.0785 (16)	0.0661 (15)	0.0294 (13)	−0.0085 (12)	−0.0115 (12)
O4	0.0839 (17)	0.0938 (18)	0.0647 (14)	0.0446 (14)	0.0324 (13)	0.0128 (12)

Geometric parameters (Å, º) top

C1—O1	1.450 (4)	C4—H4	0.9300
C1—H1A	0.9600	C5—C6	1.375 (4)
C1—H1B	0.9600	C5—H5	0.9300
C1—H1C	0.9600	C6—C7	1.402 (4)
C2—O2	1.207 (3)	C6—Cl	1.725 (3)
C2—O1	1.324 (3)	C7—C8	1.370 (4)
C2—C3	1.486 (4)	C7—N1	1.471 (3)
C3—C8	1.380 (4)	C8—H8	0.9300
C3—C4	1.402 (3)	N1—O3	1.215 (3)
C4—C5	1.376 (4)	N1—O4	1.220 (3)

O1—C1—H1A	109.5	C6—C5—H5	119.6
O1—C1—H1B	109.5	C4—C5—H5	119.6
H1A—C1—H1B	109.5	C5—C6—C7	118.1 (3)
O1—C1—H1C	109.5	C5—C6—Cl	118.7 (2)
H1A—C1—H1C	109.5	C7—C6—Cl	123.1 (2)
H1B—C1—H1C	109.5	C8—C7—C6	121.6 (2)
O2—C2—O1	123.3 (3)	C8—C7—N1	117.2 (2)
O2—C2—C3	124.1 (2)	C6—C7—N1	121.2 (2)
O1—C2—C3	112.7 (2)	C7—C8—C3	120.1 (2)
C8—C3—C4	118.7 (2)	C7—C8—H8	120.0
C8—C3—C2	118.5 (2)	C3—C8—H8	120.0
C4—C3—C2	122.8 (2)	O3—N1—O4	125.0 (3)
C5—C4—C3	120.7 (2)	O3—N1—C7	117.8 (2)
C5—C4—H4	119.6	O4—N1—C7	117.1 (2)
C3—C4—H4	119.6	C2—O1—C1	116.9 (2)
C6—C5—C4	120.8 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5···O2ⁱ	0.93	2.47	3.272 (3)	145

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

Experimental details

Crystal data
Chemical formula	C₈H₆ClNO₄
M_r	215.59
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	7.338 (1), 7.480 (1), 9.715 (2)
α, β, γ (°)	98.39 (3), 94.89 (3), 118.95 (3)
V (Å³)	454.1 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.41
Crystal size (mm)	0.40 × 0.10 × 0.10

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.854, 0.961
No. of measured, independent and observed [I > 2σ(I)] reflections	1918, 1773, 1389
R_int	0.019
(sin θ/λ)_max (Å⁻¹)	0.616

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.046, 0.142, 1.12
No. of reflections	1773
No. of parameters	128
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.21, −0.24

Computer programs: CAD-4 Software (Enraf–Nonius, 1989), XCAD4 (Harms & Wocadlo,1995), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEPIII (Burnett & Johnson, 1996), ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2003).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5···O2ⁱ	0.93	2.47	3.272 (3)	145.1

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

Acknowledgements

The authors thank the Center for Testing and Analysis, Nanjing University, for support.

References

Andrews, S. P. & Ladlow, M. (2003). J. Org. Chem. 68, 5525–5533. Web of Science CrossRef PubMed CAS Google Scholar
Burnett, M. N. & Johnson, C. K. (1996). ORTEPIII. Report ORNL-6895. Oak Ridge National Laboratory, Tennessee, USA. Google Scholar
Enraf–Nonius (1989). CAD-4 Software. Version 5.0. Enraf–Nonius, Delft, The Netherlands. Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Harms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany. Google Scholar
Jin, L.-F. & Xiao, F.-P. (2005). Acta Cryst. E61, o1237–o1238. Web of Science CSD CrossRef IUCr Journals Google Scholar
Jönssen, D., Warrington, B. H. & Ladlow, M. (2004). J. Comb. Chem. 6, 584–595. Web of Science PubMed 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
Sheldrick, G. M. (1997). SHELXL97 and SHELXS97. University of Göttingen, Germany. Google Scholar
Souza, M. V. N. de, Vasconcelos, T. R. A., Wardell, S. M. S. V., Wardell, J. L., Low, J. N. & Glidewell, C. (2006). Acta Cryst. C62, o295–o298. Web of Science CSD CrossRef IUCr Journals Google Scholar
Spek, A. L. (2003). J. Appl. Cryst. 36, 7–13. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spiniello, M. & White, J. M. (2003). Org. Biomol. Chem. 1, 3094–3096. Web of Science CSD CrossRef PubMed CAS Google Scholar