supplementary materials
Ethyl 4-anilino-3-nitrobenzoate
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.
H atoms were positioned geometrically, with N-H = 0.86 Å (for NH) and 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 Uiso(H) = xUeq(C,N),
where x = 1.5 for methyl H and x = 1.2 for all other H atoms.
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).
Ethyl 4-anilino-3-nitrobenzoate
top
Crystal data top
| C15H14N2O4 | F(000) = 600 |
| Mr = 286.28 | Dx = 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 | Rint = 0.051 |
| graphite | θmax = 25.2°, θmin = 2.2° |
| ω/2θ scans | h = −12→12 |
Absorption correction: ψ scan
(North et al., 1968) | k = 0→11 |
| Tmin = 0.971, Tmax = 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(Fo2) + (0.050P)2 + 3.4P]
where P = (Fo2 + 2Fc2)/3 |
| 2508 reflections | (Δ/σ)max < 0.001 |
| 190 parameters | Δρmax = 0.31 e Å−3 |
| 0 restraints | Δρmin = −0.32 e Å−3 |
Crystal data top
| C15H14N2O4 | V = 1399.7 (5) Å3 |
| Mr = 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) | Rint = 0.051 |
| Tmin = 0.971, Tmax = 0.980 | θmax = 25.2° |
| 2647 measured reflections | 3 standard reflections every 120 min |
| 2508 independent reflections | intensity decay: none |
Refinement top
| R[F2 > 2σ(F2)] = 0.071 | H-atom parameters constrained |
| wR(F2) = 0.199 | Δρmax = 0.31 e Å−3 |
| S = 1.00 | Δρmin = −0.32 e Å−3 |
| 2508 reflections | Absolute structure: ? |
| 190 parameters | Flack parameter: ? |
| 0 restraints | Rogers parameter: ? |
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 | Uiso*/Ueq | |
| 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, °) 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, °) 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 codes: (i) x−1/2, −y−1/2, z−1/2. |
Table 1
Hydrogen-bond geometry (Å, °) 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 codes: (i) x−1/2, −y−1/2, z−1/2. |
The authors thank Dr Shan Liu, Nanjing University of Technology, for useful
discussions and the Center of Testing and Analysis, Nanjing University, for
support.
Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, S1–S19.
Cremer, D. & Pople, J. A. (1975). J. Am. Chem. Soc. 97, 1354–1358.
Enraf–Nonius (1989). CAD-4 Software. Enraf–Nonius, Delft. The Netherlands.
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.
Harms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany.
North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
O hydrogen bond results in a non-planar six-membered ring with a flattened-boat conformation. In the crystal structure, intermolecular N-H![[pi]](/logos/entities/pi_rmgif.gif)
-![[Figure 1]](./hk2595fig1thm.gif)
![[Figure 2]](./hk2595fig2thm.gif)
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, QT, 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.