Ethyl 4-anilino-3-nitrobenzoate

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

doi:10.1107/S1600536808041329

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 65| Part 1| January 2009| Page o91

doi:10.1107/S1600536808041329

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Ethyl 4-anilino-3-nitrobenzoate

Hao-Yuan Li,^a Bo-Nian Liu,^a Shi-Gui Tang ^b 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 4 December 2008; accepted 7 December 2008; online 10 December 2008)

In the title compound, C₁₅H₁₄N₂O₄, the aromatic rings are oriented at a dihedral angle of 78.33 (3)°. An intramolecular N—H⋯O hydrogen bond results in a non-planar six-membered ring with a flattened-boat conformation. In the crystal structure, intermolecular N—H⋯O hydrogen bonds link the molecules. π–π contacts between the phenyl rings and both the phenyl and benzene rings, [centroid–centroid distances = 3.841 (3) and 3.961 (3) Å] may further stabilize the structure.

Related literature

For bond-length data, see: Allen et al. (1987 ). For ring puckering parameters, see: Cremer & Pople (1975 ).

Experimental

Crystal data

C₁₅H₁₄N₂O₄
M_r = 286.28
Monoclinic, P 2₁ /n
a = 10.683 (2) Å
b = 9.905 (2) Å
c = 13.698 (3) Å
β = 105.05 (3)°
V = 1399.7 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 294 (2) K
0.30 × 0.20 × 0.20 mm

Data collection

Enraf-Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.971, T_max = 0.980
2647 measured reflections
2508 independent reflections
1519 reflections with I > 2σ(I)
R_int = 0.051
3 standard reflections frequency: 120 min intensity decay: none

Refinement

R[F² > 2σ(F²)] = 0.071
wR(F²) = 0.199
S = 1.00
2508 reflections
190 parameters
H-atom parameters constrained
Δρ_max = 0.31 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
N2—H2A⋯O3	0.86	1.98	2.623 (5)	131
N2—H2A⋯O2ⁱ	0.86	2.31	2.978 (4)	134
Symmetry code: (i) $[x-{\script{1\over 2}}, -y-{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

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 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808041329/hk2595sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808041329/hk2595Isup2.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 (C4-C9) and B (C10-C15) are, of course, planar, and they are oriented at a dihedral angle of 78.33 (3)°. The intramolecular N-H···O hydrogen bond (Table 1) results in a nonplanar six-membered ring C (O3/N1/N2/C6/C7/H2A), having total puckering amplitude, Q_T, of 0.131 (2) Å, flattened-boat conformation [ϕ = 140.37 (3)° and θ = 75.09 (4)°] (Cremer & Pople, 1975).

In the crystal structure, intermolecular N-H···O hydrogen bonds (Table 1) link the molecules (Fig. 2), in which they may be effective in the stabilization of the structure. The π-π contacts between the phenyl rings and the phenyl and the benzene rings, Cg1—Cg1ⁱ and Cg1—Cg2ⁱⁱ [symmetry codes: (i) 1 - x, 1 - y, 1 - z; (ii) x - 1/2, 1/2 - y, z - 1/2, where Cg1 and Cg2 are centroids of the rings A (C4-C6) and B (C10-C15), respectively] may further stabilize the structure, with centroid-centroid distances of 3.841 (3) Å and 3.961 (3) Å.

Related literature top

For bond-length data, see: Allen et al. (1987). For ring puckering parameters, see: Cremer & Pople (1975).

Experimental top

For the preparation of the title compound, ethyl 4-chloro-3-nitrobenzoate (5.0 g, 0.022 mol) was heated in fresh distilled aniline (10 ml) for 18 h at 393 K, and then ethanol (50 ml) was added, at room temperature. The yellow precipitate was sucked, washed with cold ethanol (2 X 20 ml), and then dried (yield; 4.7 g, 75%). 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); 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.

Ethyl 4-anilino-3-nitrobenzoate top

Crystal data top

C₁₅H₁₄N₂O₄	F(000) = 600
M_r = 286.28	D_x = 1.358 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 25 reflections
a = 10.683 (2) Å	θ = 10–13°
b = 9.905 (2) Å	µ = 0.10 mm⁻¹
c = 13.698 (3) Å	T = 294 K
β = 105.05 (3)°	Block, colorless
V = 1399.7 (5) Å³	0.30 × 0.20 × 0.20 mm
Z = 4

Data collection top

Enraf-Nonius CAD-4 diffractometer	1519 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.051
Graphite monochromator	θ_max = 25.2°, θ_min = 2.2°
ω/2θ scans	h = −12→12
Absorption correction: ψ scan (North et al., 1968)	k = 0→11
T_min = 0.971, T_max = 0.980	l = 0→16
2647 measured reflections	3 standard reflections every 120 min
2508 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)] = 0.071	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.199	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.050P)² + 3.4P] where P = (F_o² + 2F_c²)/3
2508 reflections	(Δ/σ)_max < 0.001
190 parameters	Δρ_max = 0.31 e Å⁻³
0 restraints	Δρ_min = −0.32 e Å⁻³

Crystal data top

C₁₅H₁₄N₂O₄	V = 1399.7 (5) Å³
M_r = 286.28	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 10.683 (2) Å	µ = 0.10 mm⁻¹
b = 9.905 (2) Å	T = 294 K
c = 13.698 (3) Å	0.30 × 0.20 × 0.20 mm
β = 105.05 (3)°

Data collection top

Enraf-Nonius CAD-4 diffractometer	1519 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.051
T_min = 0.971, T_max = 0.980	3 standard reflections every 120 min
2647 measured reflections	intensity decay: none
2508 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.071	0 restraints
wR(F²) = 0.199	H-atom parameters constrained
S = 1.00	Δρ_max = 0.31 e Å⁻³
2508 reflections	Δρ_min = −0.32 e Å⁻³
190 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 refle (Sheldrick, 2008)ctions. 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	0.0229 (3)	0.1219 (3)	0.2353 (2)	0.0602 (9)
O2	0.1935 (2)	−0.0076 (3)	0.2291 (2)	0.0605 (8)
O3	−0.0506 (3)	−0.4222 (3)	−0.1083 (3)	0.0705 (10)
O4	0.1353 (3)	−0.3433 (4)	−0.0297 (3)	0.0852 (12)
N1	0.0155 (3)	−0.3404 (4)	−0.0480 (3)	0.0560 (9)
N2	−0.2640 (3)	−0.2968 (4)	−0.1003 (2)	0.0523 (9)
H2A	−0.2321	−0.3625	−0.1271	0.063*
C1	0.0290 (5)	0.2946 (6)	0.3560 (4)	0.0943 (19)
H1A	0.0836	0.3471	0.4092	0.141*
H1B	−0.0328	0.2455	0.3820	0.141*
H1C	−0.0159	0.3535	0.3027	0.141*
C2	0.1084 (4)	0.1999 (5)	0.3166 (4)	0.0683 (14)
H2B	0.1541	0.1399	0.3700	0.082*
H2C	0.1718	0.2486	0.2909	0.082*
C3	0.0774 (4)	0.0183 (4)	0.2003 (3)	0.0489 (10)
C4	−0.0131 (3)	−0.0606 (4)	0.1202 (3)	0.0464 (10)
C5	0.0350 (3)	−0.1607 (4)	0.0723 (3)	0.0452 (10)
H5A	0.1238	−0.1764	0.0897	0.054*
C6	−0.0450 (3)	−0.2399 (4)	−0.0018 (3)	0.0434 (9)
C7	−0.1821 (3)	−0.2191 (4)	−0.0295 (3)	0.0438 (9)
C8	−0.2275 (3)	−0.1155 (4)	0.0203 (3)	0.0486 (10)
H8A	−0.3161	−0.0984	0.0034	0.058*
C9	−0.1479 (3)	−0.0370 (4)	0.0934 (3)	0.0465 (10)
H9A	−0.1827	0.0313	0.1249	0.056*
C10	−0.4030 (3)	−0.2732 (5)	−0.1322 (3)	0.0526 (11)
C11	−0.4831 (4)	−0.3588 (6)	−0.1004 (4)	0.0754 (15)
H11A	−0.4487	−0.4284	−0.0559	0.090*
C12	−0.6166 (5)	−0.3428 (7)	−0.1342 (5)	0.0907 (19)
H12A	−0.6722	−0.4012	−0.1127	0.109*
C13	−0.6650 (4)	−0.2397 (7)	−0.1995 (5)	0.096 (2)
H13A	−0.7543	−0.2280	−0.2219	0.115*
C14	−0.5848 (4)	−0.1536 (6)	−0.2324 (4)	0.0854 (18)
H14A	−0.6199	−0.0841	−0.2768	0.103*
C15	−0.4501 (4)	−0.1691 (5)	−0.1999 (4)	0.0654 (13)
H15B	−0.3944	−0.1122	−0.2226	0.078*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0423 (16)	0.0602 (19)	0.0576 (18)	−0.0073 (14)	−0.0236 (13)	−0.0105 (15)
O2	0.0306 (14)	0.075 (2)	0.0604 (18)	−0.0033 (14)	−0.0167 (12)	0.0023 (16)
O3	0.0482 (17)	0.067 (2)	0.080 (2)	0.0093 (16)	−0.0131 (16)	−0.0220 (18)
O4	0.0283 (15)	0.115 (3)	0.104 (3)	0.0123 (17)	0.0021 (16)	−0.016 (2)
N1	0.0367 (18)	0.069 (2)	0.056 (2)	0.0118 (18)	−0.0003 (16)	−0.0016 (19)
N2	0.0263 (16)	0.066 (2)	0.056 (2)	−0.0001 (15)	−0.0046 (14)	−0.0167 (18)
C1	0.090 (4)	0.092 (4)	0.082 (4)	−0.013 (3)	−0.013 (3)	−0.026 (3)
C2	0.057 (3)	0.068 (3)	0.061 (3)	−0.013 (2)	−0.018 (2)	−0.017 (3)
C3	0.040 (2)	0.053 (3)	0.042 (2)	−0.0083 (19)	−0.0115 (17)	0.009 (2)
C4	0.0278 (18)	0.052 (2)	0.045 (2)	−0.0041 (17)	−0.0165 (16)	0.0055 (19)
C5	0.0262 (18)	0.052 (2)	0.046 (2)	−0.0026 (17)	−0.0117 (16)	0.0101 (19)
C6	0.0299 (18)	0.053 (2)	0.041 (2)	0.0049 (17)	−0.0023 (16)	0.0030 (18)
C7	0.0240 (17)	0.049 (2)	0.048 (2)	−0.0009 (17)	−0.0090 (15)	−0.0001 (19)
C8	0.0233 (17)	0.060 (3)	0.053 (2)	0.0000 (17)	−0.0071 (16)	−0.001 (2)
C9	0.0327 (19)	0.052 (2)	0.047 (2)	−0.0006 (17)	−0.0021 (16)	−0.0051 (19)
C10	0.0226 (18)	0.068 (3)	0.057 (3)	−0.0039 (19)	−0.0082 (17)	−0.023 (2)
C11	0.047 (3)	0.107 (4)	0.072 (3)	−0.015 (3)	0.014 (2)	−0.016 (3)
C12	0.048 (3)	0.118 (5)	0.114 (5)	−0.026 (3)	0.036 (3)	−0.033 (4)
C13	0.024 (2)	0.127 (6)	0.122 (5)	−0.009 (3)	−0.006 (3)	−0.064 (5)
C14	0.039 (3)	0.098 (4)	0.097 (4)	0.016 (3)	−0.022 (3)	−0.030 (3)
C15	0.033 (2)	0.059 (3)	0.089 (3)	0.002 (2)	−0.013 (2)	−0.008 (3)

Geometric parameters (Å, º) top

O1—C2	1.463 (5)	C5—C6	1.387 (5)
O1—C3	1.329 (5)	C5—H5A	0.9300
O2—C3	1.227 (4)	C6—C7	1.429 (5)
N1—O3	1.239 (4)	C7—C8	1.387 (5)
N1—O4	1.240 (4)	C8—C9	1.374 (5)
N1—C6	1.422 (5)	C8—H8A	0.9300
N2—C7	1.363 (5)	C9—H9A	0.9300
N2—C10	1.454 (4)	C10—C11	1.354 (6)
N2—H2A	0.8600	C10—C15	1.390 (6)
C1—C2	1.458 (7)	C11—C12	1.390 (7)
C1—H1A	0.9600	C11—H11A	0.9300
C1—H1B	0.9600	C12—C13	1.367 (9)
C1—H1C	0.9600	C12—H12A	0.9300
C2—H2B	0.9700	C13—C14	1.366 (8)
C2—H2C	0.9700	C13—H13A	0.9300
C3—C4	1.483 (5)	C14—C15	1.400 (6)
C4—C5	1.360 (6)	C14—H14A	0.9300
C4—C9	1.410 (5)	C15—H15B	0.9300

C3—O1—C2	115.9 (3)	C5—C6—N1	117.2 (3)
O3—N1—O4	120.0 (4)	C5—C6—C7	120.5 (4)
O3—N1—C6	120.6 (3)	N2—C7—C8	121.7 (3)
O4—N1—C6	119.4 (4)	N2—C7—C6	122.1 (4)
C7—N2—C10	122.7 (3)	C8—C7—C6	116.1 (3)
C7—N2—H2A	118.7	C7—C8—H8A	118.4
C10—N2—H2A	118.7	C9—C8—C7	123.2 (3)
C2—C1—H1A	109.5	C9—C8—H8A	118.4
C2—C1—H1B	109.5	C4—C9—H9A	120.3
C2—C1—H1C	109.5	C8—C9—C4	119.5 (4)
H1A—C1—H1B	109.5	C8—C9—H9A	120.3
H1A—C1—H1C	109.5	C11—C10—C15	122.0 (4)
H1B—C1—H1C	109.5	C11—C10—N2	118.9 (4)
O1—C2—H2B	110.0	C15—C10—N2	119.0 (4)
O1—C2—H2C	110.0	C10—C11—C12	120.1 (6)
C1—C2—O1	108.3 (4)	C10—C11—H11A	120.0
C1—C2—H2B	110.0	C12—C11—H11A	120.0
C1—C2—H2C	110.0	C11—C12—H12A	120.5
H2B—C2—H2C	108.4	C13—C12—C11	118.9 (5)
O1—C3—C4	114.3 (3)	C13—C12—H12A	120.5
O2—C3—O1	123.1 (4)	C12—C13—H13A	119.4
O2—C3—C4	122.6 (4)	C14—C13—C12	121.3 (5)
C5—C4—C9	118.9 (3)	C14—C13—H13A	119.4
C5—C4—C3	119.0 (3)	C13—C14—C15	120.5 (6)
C9—C4—C3	122.1 (4)	C13—C14—H14A	119.8
C4—C5—C6	121.8 (3)	C15—C14—H14A	119.8
C4—C5—H5A	119.1	C10—C15—C14	117.2 (5)
C6—C5—H5A	119.1	C10—C15—H15B	121.4
N1—C6—C7	122.4 (3)	C14—C15—H15B	121.4

C3—O1—C2—C1	−171.2 (4)	N1—C6—C7—N2	1.8 (6)
C2—O1—C3—O2	−4.1 (6)	C5—C6—C7—C8	1.1 (6)
C2—O1—C3—C4	178.3 (4)	N1—C6—C7—C8	−178.6 (4)
O2—C3—C4—C5	−3.9 (6)	N2—C7—C8—C9	178.7 (4)
O1—C3—C4—C5	173.7 (4)	C6—C7—C8—C9	−0.9 (6)
O2—C3—C4—C9	174.8 (4)	C7—C8—C9—C4	0.1 (6)
O1—C3—C4—C9	−7.6 (5)	C5—C4—C9—C8	0.4 (6)
C9—C4—C5—C6	−0.2 (6)	C3—C4—C9—C8	−178.4 (4)
C3—C4—C5—C6	178.6 (4)	C7—N2—C10—C11	−106.2 (5)
C4—C5—C6—N1	179.1 (4)	C7—N2—C10—C15	78.1 (5)
C4—C5—C6—C7	−0.6 (6)	C15—C10—C11—C12	−1.0 (7)
O3—N1—C6—C5	173.7 (4)	N2—C10—C11—C12	−176.6 (4)
O4—N1—C6—C5	−8.2 (6)	C10—C11—C12—C13	−0.1 (8)
O3—N1—C6—C7	−6.6 (6)	C11—C12—C13—C14	0.5 (9)
O4—N1—C6—C7	171.5 (4)	C12—C13—C14—C15	0.1 (8)
C10—N2—C7—C8	3.1 (6)	C11—C10—C15—C14	1.6 (7)
C10—N2—C7—C6	−177.4 (4)	N2—C10—C15—C14	177.2 (4)
C5—C6—C7—N2	−178.5 (4)	C13—C14—C15—C10	−1.1 (7)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O3	0.86	1.98	2.623 (5)	131
N2—H2A···O2ⁱ	0.86	2.31	2.978 (4)	134

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

Experimental details

Crystal data
Chemical formula	C₁₅H₁₄N₂O₄
M_r	286.28
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	294
a, b, c (Å)	10.683 (2), 9.905 (2), 13.698 (3)
β (°)	105.05 (3)
V (Å³)	1399.7 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.30 × 0.20 × 0.20

Data collection
Diffractometer	Enraf-Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.971, 0.980
No. of measured, independent and observed [I > 2σ(I)] reflections	2647, 2508, 1519
R_int	0.051
(sin θ/λ)_max (Å⁻¹)	0.598

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.071, 0.199, 1.00
No. of reflections	2508
No. of parameters	190
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.31, −0.32

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O3	0.86	1.98	2.623 (5)	131
N2—H2A···O2ⁱ	0.86	2.31	2.978 (4)	134

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

Acknowledgements

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

References

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