Methyl 4-anilino-3-nitro­benzoate

Li, H.-Y.; Wu, Y.-Z.; Liu, B.-N.; Tang, S.-G.; Guo, C.

doi:10.1107/S1600536809018923

organic compounds

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ISSN: 2056-9890

Volume 65| Part 6| June 2009| Page o1381

doi:10.1107/S1600536809018923

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Methyl 4-anilino-3-nitrobenzoate

Hao-Yuan Li,^a Yong-Zhong Wu,^b Bo-Nian Liu,^c Shi-Gui Tang ^a and Cheng Guo ^c ^*

^aCollege of Biotechnology and Pharmaceutical Engineering, Nanjing University of Technology, Xinmofan Road No. 5 Nanjing, Nanjing 210009, People's Republic of China, ^bDepartment of Applied Chemistry, Nanjing College of Chemical Technology, Geguan Road No. 625 Dachang District Nanjing, Nanjing 210048, People's Republic of China, and ^cCollege of Science, Nanjing University of Technology, Xinmofan Road No. 5 Nanjing, Nanjing 210009, People's Republic of China
^*Correspondence e-mail: guocheng@njut.edu.cn

(Received 14 May 2009; accepted 19 May 2009; online 23 May 2009)

In the molecule of the title compound, C₁₄H₁₂N₂O₄, the aromatic rings are oriented at a dihedral angle of 51.50 (4)°. An intramolecular N—H⋯O interaction results in the formation of a six-membered ring having an envelope conformation. In the crystal structure, intermolecular N—H⋯O interactions link the molecules into centrosymmetric dimers. π–π contacts between the benzene rings [centroid–centroid distance = 3.708 (1) Å] may further stabilize the structure.

Related literature

For bond-length data, see: Allen et al. (1987 ). For the synthesis, see: Schelz (1978 ).

Experimental

Crystal data

C₁₄H₁₂N₂O₄
M_r = 272.26
Monoclinic, P 2₁ /c
a = 11.641 (2) Å
b = 16.349 (3) Å
c = 7.2490 (14) Å
β = 107.50 (3)°
V = 1315.8 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 294 K
0.30 × 0.20 × 0.10 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.970, T_max = 0.990
2569 measured reflections
2367 independent reflections
1335 reflections with I > 2σ(I)
R_int = 0.026
3 standard reflections frequency: 120 min intensity decay: 1%

Refinement

R[F² > 2σ(F²)] = 0.066
wR(F²) = 0.178
S = 1.00
2367 reflections
175 parameters
H-atom parameters constrained
Δρ_max = 0.33 e Å⁻³
Δρ_min = −0.44 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O1	0.86	2.01	2.650 (4)	130
N1—H1A⋯O1ⁱ	0.86	2.53	3.314 (4)	152
Symmetry code: (i) -x, -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, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ) and PLATON (Spek, 2009 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809018923/hk2689sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809018923/hk2689Isup2.hkl

checkCIF report

Comment top

Some derivatives of benzoic acid are important chemical materials. We report herein the crystal structure of the title compound.

In the molecule of the title compound (Fig 1), the bond lengths (Allen et al., 1987) and angles are within normal ranges. Rings A (C1-C6) and B (C7-C12) are, of course, planar and they are oriented at a dihedral angle of A/B = 51.50 (4)°. Intramolecular N-H···O interaction (Table 1) results in the formation of a six-membered ring C (O1/N1/N2/C7/C12/H1A) having envelope conformation with atom O1 displaced by 0.125 (4) Å from the plane of the other ring atoms.

In the crystal structure, intra- and intermolecular N-H···O interactions (Table 1) link the molecules into centrosymmetric dimers (Fig. 2), in which they may be effective in the stabilization of the structure. The π–π contact between the benzene rings, Cg2—Cg2ⁱ [symmetry code: (i) x, 1/2 - y, z - 1/2, where Cg2 is centroid of the ring B (C7-C12)] may further stabilize the structure, with centroid-centroid distance of 3.708 (1) Å.

Related literature top

For bond-length data, see: Allen et al. (1987). For the synthesis, see: Schelz (1978).

Experimental top

For the preparation of the title compound, methyl 4-chloro-3-nitrobenzoate (5.0 g, 23 mmol) was heated in distilled aniline (10 ml) for 18 h at 393 K. After the reaction was completed, ethanol (50 ml) was added, at room temperature. The yellow precipitate was washed with cold ethanol (2 × 20 ml), and then dried (yield; 4.7 g). Crystals suitable for X-ray analysis were obtained by slow evaporation of an ethanol 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: ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme. Hydrogen bond is shown as dashed line.
	Fig. 2. A partial packing diagram of the title compound. Hydrogen bonds are shown as dashed lines.

Methyl 4-anilino-3-nitrobenzoate top

Crystal data top

C₁₄H₁₂N₂O₄	F(000) = 568
M_r = 272.26	D_x = 1.374 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 25 reflections
a = 11.641 (2) Å	θ = 10–12°
b = 16.349 (3) Å	µ = 0.10 mm⁻¹
c = 7.2490 (14) Å	T = 294 K
β = 107.50 (3)°	Block, colorless
V = 1315.8 (5) Å³	0.30 × 0.20 × 0.10 mm
Z = 4

Data collection top

Enraf–Nonius CAD-4 diffractometer	1335 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.026
Graphite monochromator	θ_max = 25.2°, θ_min = 1.8°
ω/2θ scans	h = −13→13
Absorption correction: ψ scan (North et al., 1968)	k = −19→0
T_min = 0.970, T_max = 0.990	l = 0→8
2569 measured reflections	3 standard reflections every 120 min
2367 independent reflections	intensity decay: 1%

Refinement top

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)] = 0.066	H-atom parameters constrained
wR(F²) = 0.178	w = 1/[σ²(F_o²) + (0.08P)² + 0.4P] where P = (F_o² + 2F_c²)/3
S = 1.00	(Δ/σ)_max < 0.001
2367 reflections	Δρ_max = 0.33 e Å⁻³
175 parameters	Δρ_min = −0.44 e Å⁻³
Primary atom site location: structure-invariant direct methods

Crystal data top

C₁₄H₁₂N₂O₄	V = 1315.8 (5) Å³
M_r = 272.26	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 11.641 (2) Å	µ = 0.10 mm⁻¹
b = 16.349 (3) Å	T = 294 K
c = 7.2490 (14) Å	0.30 × 0.20 × 0.10 mm
β = 107.50 (3)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	1335 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.026
T_min = 0.970, T_max = 0.990	3 standard reflections every 120 min
2569 measured reflections	intensity decay: 1%
2367 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.066	175 parameters
wR(F²) = 0.178	H-atom parameters constrained
S = 1.00	Δρ_max = 0.33 e Å⁻³
2367 reflections	Δρ_min = −0.44 e Å⁻³

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
O1	0.0837 (2)	0.05896 (17)	0.1085 (4)	0.078
O2	0.2328 (2)	0.11328 (16)	0.2971 (4)	0.0677 (9)
O3	0.1608 (3)	0.48217 (18)	0.1788 (5)	0.0848 (10)
O4	0.2843 (2)	0.39247 (16)	0.3690 (4)	0.0648 (8)
N1	−0.1155 (2)	0.14101 (18)	−0.0669 (4)	0.0501 (8)
H1A	−0.0836	0.0932	−0.0446	0.060*
N2	0.1335 (3)	0.11733 (17)	0.1801 (5)	0.0479 (8)
C1	−0.4811 (4)	0.1408 (3)	−0.3820 (7)	0.0754 (14)
H1B	−0.5621	0.1397	−0.4538	0.091*
C2	−0.4423 (4)	0.1887 (3)	−0.2185 (7)	0.0721 (13)
H2A	−0.4973	0.2200	−0.1789	0.087*
C3	−0.3218 (3)	0.1902 (3)	−0.1139 (6)	0.0575 (11)
H3A	−0.2959	0.2222	−0.0031	0.069*
C4	−0.2393 (3)	0.1441 (2)	−0.1731 (5)	0.0440 (9)
C5	−0.2794 (3)	0.0959 (2)	−0.3384 (5)	0.0504 (10)
H5A	−0.2254	0.0647	−0.3808	0.061*
C6	−0.3991 (4)	0.0951 (3)	−0.4367 (6)	0.0638 (12)
H6A	−0.4259	0.0621	−0.5457	0.077*
C7	−0.0420 (3)	0.2050 (2)	0.0031 (5)	0.0378 (8)
C8	−0.0795 (3)	0.2868 (2)	−0.0439 (5)	0.0460 (9)
H8A	−0.1567	0.2963	−0.1260	0.055*
C9	−0.0075 (3)	0.3514 (2)	0.0258 (5)	0.0465 (9)
H9A	−0.0363	0.4039	−0.0101	0.056*
C10	0.1095 (3)	0.3414 (2)	0.1510 (5)	0.0431 (9)
C11	0.1507 (3)	0.2631 (2)	0.1962 (5)	0.0416 (9)
H11A	0.2284	0.2549	0.2777	0.050*
C12	0.0786 (3)	0.1958 (2)	0.1226 (5)	0.0385 (8)
C13	0.1830 (4)	0.4131 (2)	0.2287 (6)	0.0509 (10)
C14	0.3604 (4)	0.4579 (3)	0.4546 (7)	0.0886 (16)
H14A	0.4293	0.4372	0.5528	0.133*
H14B	0.3174	0.4954	0.5116	0.133*
H14C	0.3865	0.4858	0.3576	0.133*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.064	0.060	0.091	0.006	−0.005	0.000
O2	0.0506 (16)	0.0573 (18)	0.075 (2)	0.0069 (14)	−0.0122 (15)	−0.0036 (15)
O3	0.090 (2)	0.0424 (18)	0.108 (3)	−0.0121 (16)	0.009 (2)	0.0030 (17)
O4	0.0496 (16)	0.0559 (18)	0.078 (2)	−0.0124 (13)	0.0026 (15)	−0.0116 (15)
N1	0.0426 (17)	0.0421 (17)	0.056 (2)	−0.0071 (14)	0.0013 (15)	−0.0022 (15)
N2	0.0406 (17)	0.0336 (16)	0.058 (2)	−0.0125 (13)	−0.0025 (16)	−0.0141 (14)
C1	0.045 (2)	0.082 (3)	0.082 (3)	−0.021 (2)	−0.007 (2)	0.010 (3)
C2	0.044 (2)	0.086 (3)	0.086 (4)	−0.006 (2)	0.017 (2)	−0.007 (3)
C3	0.044 (2)	0.071 (3)	0.053 (3)	−0.010 (2)	0.0090 (19)	−0.012 (2)
C4	0.040 (2)	0.044 (2)	0.042 (2)	−0.0085 (17)	0.0045 (17)	0.0034 (17)
C5	0.053 (2)	0.046 (2)	0.046 (2)	−0.0152 (18)	0.0058 (19)	−0.0013 (18)
C6	0.061 (3)	0.071 (3)	0.049 (3)	−0.021 (2)	0.000 (2)	−0.001 (2)
C7	0.0369 (18)	0.043 (2)	0.0349 (19)	−0.0075 (16)	0.0124 (15)	−0.0044 (16)
C8	0.039 (2)	0.054 (2)	0.043 (2)	−0.0007 (17)	0.0093 (17)	0.0032 (18)
C9	0.047 (2)	0.038 (2)	0.054 (2)	0.0001 (17)	0.0157 (18)	0.0050 (18)
C10	0.047 (2)	0.044 (2)	0.042 (2)	−0.0069 (17)	0.0171 (17)	−0.0040 (17)
C11	0.0335 (18)	0.051 (2)	0.039 (2)	−0.0018 (16)	0.0094 (16)	−0.0036 (17)
C12	0.0343 (18)	0.0368 (19)	0.044 (2)	−0.0010 (15)	0.0115 (16)	−0.0030 (16)
C13	0.058 (2)	0.042 (2)	0.057 (3)	−0.0085 (19)	0.022 (2)	−0.0058 (19)
C14	0.068 (3)	0.090 (4)	0.096 (4)	−0.037 (3)	0.006 (3)	−0.029 (3)

Geometric parameters (Å, º) top

O1—N2	1.155 (3)	C5—C6	1.361 (5)
O2—N2	1.213 (3)	C5—H5A	0.9300
O3—C13	1.190 (5)	C6—H6A	0.9300
O4—C13	1.348 (4)	C7—C8	1.416 (5)
O4—C14	1.409 (5)	C7—C12	1.419 (4)
N1—C7	1.349 (4)	C8—C9	1.348 (5)
N1—C4	1.416 (4)	C8—H8A	0.9300
N1—H1A	0.8600	C9—C10	1.401 (5)
N2—C12	1.438 (4)	C9—H9A	0.9300
C1—C6	1.361 (6)	C10—C11	1.372 (5)
C1—C2	1.378 (6)	C10—C13	1.461 (5)
C1—H1B	0.9300	C11—C12	1.389 (4)
C2—C3	1.379 (5)	C11—H11A	0.9300
C2—H2A	0.9300	C14—H14A	0.9600
C3—C4	1.387 (5)	C14—H14B	0.9600
C3—H3A	0.9300	C14—H14C	0.9600
C4—C5	1.392 (5)

C13—O4—C14	115.7 (3)	N1—C7—C12	123.1 (3)
C7—N1—C4	127.1 (3)	C8—C7—C12	115.0 (3)
C7—N1—H1A	116.5	C9—C8—C7	122.6 (3)
C4—N1—H1A	116.5	C9—C8—H8A	118.7
O1—N2—O2	120.9 (3)	C7—C8—H8A	118.7
O1—N2—C12	119.2 (3)	C8—C9—C10	121.6 (3)
O2—N2—C12	119.9 (3)	C8—C9—H9A	119.2
C6—C1—C2	119.0 (4)	C10—C9—H9A	119.2
C6—C1—H1B	120.5	C11—C10—C9	117.8 (3)
C2—C1—H1B	120.5	C11—C10—C13	122.3 (3)
C1—C2—C3	119.9 (4)	C9—C10—C13	119.9 (3)
C1—C2—H2A	120.1	C10—C11—C12	121.3 (3)
C3—C2—H2A	120.1	C10—C11—H11A	119.3
C2—C3—C4	120.3 (4)	C12—C11—H11A	119.3
C2—C3—H3A	119.8	C11—C12—C7	121.5 (3)
C4—C3—H3A	119.8	C11—C12—N2	115.5 (3)
C3—C4—C5	119.3 (3)	C7—C12—N2	122.9 (3)
C3—C4—N1	122.6 (3)	O3—C13—O4	121.9 (4)
C5—C4—N1	118.1 (3)	O3—C13—C10	126.6 (4)
C6—C5—C4	118.7 (4)	O4—C13—C10	111.6 (3)
C6—C5—H5A	120.6	O4—C14—H14A	109.5
C4—C5—H5A	120.6	O4—C14—H14B	109.5
C5—C6—C1	122.7 (4)	H14A—C14—H14B	109.5
C5—C6—H6A	118.7	O4—C14—H14C	109.5
C1—C6—H6A	118.7	H14A—C14—H14C	109.5
N1—C7—C8	121.8 (3)	H14B—C14—H14C	109.5

C6—C1—C2—C3	0.3 (7)	C13—C10—C11—C12	179.1 (4)
C1—C2—C3—C4	0.5 (7)	C10—C11—C12—C7	−2.3 (5)
C2—C3—C4—C5	−0.5 (6)	C10—C11—C12—N2	179.4 (3)
C2—C3—C4—N1	−177.5 (4)	N1—C7—C12—C11	−178.3 (3)
C7—N1—C4—C3	−48.9 (5)	C8—C7—C12—C11	3.8 (5)
C7—N1—C4—C5	134.0 (4)	N1—C7—C12—N2	−0.1 (5)
C3—C4—C5—C6	−0.3 (6)	C8—C7—C12—N2	−178.0 (3)
N1—C4—C5—C6	176.9 (3)	O1—N2—C12—C11	−171.9 (4)
C4—C5—C6—C1	1.2 (6)	O2—N2—C12—C11	5.4 (5)
C2—C1—C6—C5	−1.2 (7)	O1—N2—C12—C7	9.8 (6)
C4—N1—C7—C8	−7.9 (6)	O2—N2—C12—C7	−172.9 (3)
C4—N1—C7—C12	174.4 (3)	C14—O4—C13—O3	1.2 (6)
N1—C7—C8—C9	179.6 (4)	C14—O4—C13—C10	−179.3 (4)
C12—C7—C8—C9	−2.5 (5)	C11—C10—C13—O3	169.8 (4)
C7—C8—C9—C10	−0.3 (6)	C9—C10—C13—O3	−10.4 (6)
C8—C9—C10—C11	2.1 (6)	C11—C10—C13—O4	−9.8 (5)
C8—C9—C10—C13	−177.8 (3)	C9—C10—C13—O4	170.1 (3)
C9—C10—C11—C12	−0.8 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1	0.86	2.01	2.650 (4)	130
N1—H1A···O1ⁱ	0.86	2.53	3.314 (4)	152

Symmetry code: (i) −x, −y, −z.

Experimental details

Crystal data
Chemical formula	C₁₄H₁₂N₂O₄
M_r	272.26
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	294
a, b, c (Å)	11.641 (2), 16.349 (3), 7.2490 (14)
β (°)	107.50 (3)
V (Å³)	1315.8 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.30 × 0.20 × 0.10

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.970, 0.990
No. of measured, independent and observed [I > 2σ(I)] reflections	2569, 2367, 1335
R_int	0.026
(sin θ/λ)_max (Å⁻¹)	0.599

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.066, 0.178, 1.00
No. of reflections	2367
No. of parameters	175
No. of restraints	?
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.33, −0.44

Computer programs: CAD-4 Software (Enraf–Nonius, 1989), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1	0.86	2.01	2.650 (4)	130
N1—H1A···O1ⁱ	0.86	2.53	3.314 (4)	152

Symmetry code: (i) −x, −y, −z.

Acknowledgements

The authors thank 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. 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
North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359. CrossRef IUCr Journals Web of Science Google Scholar
Schelz, D. (1978). Helv. Chim. Acta, 61, 2452–2462. CrossRef CAS Web of Science Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar