Methyl 4-anilino-3-nitro-benzoate.

In the mol-ecule of the title compound, C(14)H(12)N(2)O(4), the aromatic rings are oriented at a dihedral angle of 51.50 (4)°. An intra-molecular N-H⋯O inter-action results in the formation of a six-membered ring having an envelope conformation. In the crystal structure, inter-molecular N-H⋯O inter-actions link the mol-ecules 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 = 272.26

Monoclinic,

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[F 2 > 2σ(F 2)] = 0.066

wR(F 2) = 0.178

S = 1.00

2367 reflections

175 parameters

H-atom parameters constrained

Δρmax = 0.33 e Å−3

Δρmin = −0.44 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: ORTEP-3 for Windows (Farrugia, 1997 ▶) and PLATON (Spek, 2009 ▶); software used to prepare material for publication: SHELXL97.

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

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

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

C14H12N2O4	F(000) = 568
Mr = 272.26	Dx = 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

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

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(Fo2) + (0.08P)2 + 0.4P] where P = (Fo2 + 2Fc2)/3
S = 1.00	(Δ/σ)max < 0.001
2367 reflections	Δρmax = 0.33 e Å−3
175 parameters	Δρmin = −0.44 e Å−3
Primary atom site location: structure-invariant direct methods

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.

	x	y	z	Uiso*/Ueq
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*

	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)

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)

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

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) .