Acta Cryst. (2012). E68, o129 [ doi:10.1107/S1600536811053074 ]
The title molecule, C16H13N3O7, is slightly twisted, with the dihedral angle between the two benzene ring planes being 17.4 (1)°. An intramolecular N-H
O hydrogen bond is observed. In the crystal, weak C-HO hydrogen bonds link the molecules into chains along the b axis.
To a 250 ml round flask fitted with a condenser ethyl ortho-amino benzoate (0.1 mol), dichloromethane (15 ml) and triethylamine (0.5 ml) was added under stirring. 3,5-dinitroenzoyl chloride (0.1 mol) was added gradually. The reaction mixture was stirred at room temperature for 1 h and then refluxed for 2 h. The product precipitated as a colourless powder, which was washed three times with water and dichloromethane. Recrystallization from ethyl acetate produced the crystals of the title compound.
The structure was solved by direct methods (SHELXS97, Sheldrick, 2008) and expanded using Fourier techniques. All non-H atoms were refined anisotropically.
All H atoms are observable from difference Fourier map but were refined riding at idealized geometrical positions with C—H = 0.93, 0.96 and 0.97Å for phenyl, methyl and methylene H-atoms and N—H = 0.86 Å and Uiso(H) = 1.2Ueq(C / N) and Uiso(H) = 1.5Ueq(C-methyl).
Data collection: APEX2 (Bruker, 2007); cell refinement: APEX2 (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).
![[Figure 1]](./fk2047fig1thm.gif)
| Fig. 1. Molecular structure of the title compound with displacement ellipsoids at the 50% probability level. |
![[Figure 2]](./fk2047fig2thm.gif)
| Fig. 2. The packing diagram of the compound projected along the c-axis. |
| C16H13N3O7 | F(000) = 744 |
| Mr = 359.29 | Dx = 1.463 Mg m−3 |
| Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -P 2ybc | Cell parameters from 16092 reflections |
| a = 12.4662 (4) Å | θ = 2.8–25.0° |
| b = 17.7213 (5) Å | µ = 0.12 mm−1 |
| c = 7.4352 (2) Å | T = 296 K |
| β = 96.658 (2)° | Block, colourless |
| V = 1631.49 (8) Å3 | 0.52 × 0.30 × 0.26 mm |
| Z = 4 |
| Bruker APEXII CCD diffractometer | 2808 independent reflections |
| Radiation source: fine-focus sealed tube | 1961 reflections with I > 2σ(I) |
| graphite | Rint = 0.040 |
| ω and φ scan | θmax = 25.0°, θmin = 2.8° |
| Absorption correction: multi-scan (SADABS; Sheldrick, 2004) | h = −14→14 |
| Tmin = 0.942, Tmax = 0.970 | k = −21→21 |
| 16092 measured reflections | l = −8→8 |
| 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)] = 0.049 | H-atom parameters constrained |
| wR(F2) = 0.174 | w = 1/[σ2(Fo2) + (0.0679P)2 + 0.9448P] where P = (Fo2 + 2Fc2)/3 |
| S = 1.11 | (Δ/σ)max < 0.001 |
| 2808 reflections | Δρmax = 0.18 e Å−3 |
| 237 parameters | Δρmin = −0.22 e Å−3 |
| 0 restraints | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
| Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.013 (2) |
| C16H13N3O7 | V = 1631.49 (8) Å3 |
| Mr = 359.29 | Z = 4 |
| Monoclinic, P21/c | Mo Kα radiation |
| a = 12.4662 (4) Å | µ = 0.12 mm−1 |
| b = 17.7213 (5) Å | T = 296 K |
| c = 7.4352 (2) Å | 0.52 × 0.30 × 0.26 mm |
| β = 96.658 (2)° |
| Bruker APEXII CCD diffractometer | 2808 independent reflections |
| Absorption correction: multi-scan (SADABS; Sheldrick, 2004) | 1961 reflections with I > 2σ(I) |
| Tmin = 0.942, Tmax = 0.970 | Rint = 0.040 |
| 16092 measured reflections | θmax = 25.0° |
| R[F2 > 2σ(F2)] = 0.049 | H-atom parameters constrained |
| wR(F2) = 0.174 | Δρmax = 0.18 e Å−3 |
| S = 1.11 | Δρmin = −0.22 e Å−3 |
| 2808 reflections | Absolute structure: ? |
| 237 parameters | Flack parameter: ? |
| 0 restraints | Rogers parameter: ? |
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 | 0.66429 (15) | 0.10807 (11) | 0.9056 (3) | 0.0724 (6) | |
| O2 | 0.49758 (15) | 0.11624 (11) | 0.7638 (3) | 0.0678 (6) | |
| O3 | 0.29471 (18) | −0.10623 (12) | 0.5275 (3) | 0.0855 (7) | |
| O4 | −0.03437 (19) | −0.05325 (16) | 0.1499 (3) | 0.0870 (7) | |
| O5 | −0.11189 (19) | 0.05489 (17) | 0.1563 (4) | 0.1005 (9) | |
| O6 | 0.0466 (2) | 0.24889 (16) | 0.5560 (5) | 0.1221 (11) | |
| O7 | 0.19530 (19) | 0.22737 (13) | 0.7234 (4) | 0.0908 (8) | |
| N1 | 0.40070 (16) | −0.01091 (13) | 0.6539 (3) | 0.0560 (6) | |
| H1 | 0.4020 | 0.0374 | 0.6654 | 0.067* | |
| N2 | −0.0365 (2) | 0.01221 (19) | 0.2005 (3) | 0.0721 (7) | |
| N3 | 0.1241 (2) | 0.20962 (15) | 0.6060 (4) | 0.0752 (7) | |
| C1 | 0.5738 (2) | 0.07809 (15) | 0.8276 (3) | 0.0540 (6) | |
| C2 | 0.57853 (19) | −0.00579 (14) | 0.8223 (3) | 0.0496 (6) | |
| C3 | 0.6705 (2) | −0.04275 (16) | 0.9032 (4) | 0.0585 (7) | |
| H3 | 0.7267 | −0.0147 | 0.9634 | 0.070* | |
| C4 | 0.6794 (2) | −0.12038 (17) | 0.8952 (4) | 0.0691 (8) | |
| H4 | 0.7408 | −0.1446 | 0.9502 | 0.083* | |
| C5 | 0.5968 (3) | −0.16112 (17) | 0.8055 (5) | 0.0763 (9) | |
| H5 | 0.6032 | −0.2133 | 0.7988 | 0.092* | |
| C6 | 0.5043 (2) | −0.12685 (16) | 0.7246 (4) | 0.0676 (8) | |
| H6 | 0.4491 | −0.1559 | 0.6648 | 0.081* | |
| C7 | 0.4936 (2) | −0.04870 (15) | 0.7326 (3) | 0.0524 (6) | |
| C8 | 0.3099 (2) | −0.03932 (16) | 0.5632 (4) | 0.0582 (7) | |
| C9 | 0.22294 (19) | 0.01719 (15) | 0.5044 (3) | 0.0518 (6) | |
| C10 | 0.1393 (2) | −0.00719 (16) | 0.3779 (3) | 0.0560 (7) | |
| H10 | 0.1405 | −0.0555 | 0.3293 | 0.067* | |
| C11 | 0.0544 (2) | 0.04096 (18) | 0.3248 (3) | 0.0588 (7) | |
| C12 | 0.0482 (2) | 0.11277 (17) | 0.3938 (4) | 0.0627 (7) | |
| H12 | −0.0095 | 0.1446 | 0.3568 | 0.075* | |
| C13 | 0.1312 (2) | 0.13480 (15) | 0.5197 (4) | 0.0587 (7) | |
| C14 | 0.2185 (2) | 0.08975 (15) | 0.5764 (4) | 0.0545 (6) | |
| H14 | 0.2736 | 0.1073 | 0.6611 | 0.065* | |
| C15 | 0.6721 (3) | 0.19029 (18) | 0.9047 (6) | 0.0866 (10) | |
| H15A | 0.6505 | 0.2096 | 0.7838 | 0.104* | |
| H15B | 0.6251 | 0.2119 | 0.9863 | 0.104* | |
| C16 | 0.7843 (3) | 0.2102 (2) | 0.9632 (9) | 0.139 (2) | |
| H16A | 0.7925 | 0.2640 | 0.9594 | 0.208* | |
| H16B | 0.8302 | 0.1870 | 0.8841 | 0.208* | |
| H16C | 0.8039 | 0.1926 | 1.0847 | 0.208* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| O1 | 0.0586 (11) | 0.0578 (12) | 0.0953 (15) | −0.0026 (9) | −0.0149 (10) | −0.0026 (10) |
| O2 | 0.0540 (11) | 0.0594 (11) | 0.0863 (14) | 0.0043 (9) | −0.0075 (10) | 0.0016 (10) |
| O3 | 0.0770 (14) | 0.0613 (13) | 0.1109 (18) | −0.0009 (11) | −0.0198 (13) | −0.0172 (12) |
| O4 | 0.0805 (15) | 0.1026 (19) | 0.0738 (15) | −0.0281 (14) | −0.0077 (11) | −0.0029 (13) |
| O5 | 0.0623 (14) | 0.135 (2) | 0.0963 (18) | 0.0002 (14) | −0.0259 (13) | 0.0126 (16) |
| O6 | 0.0978 (19) | 0.101 (2) | 0.158 (3) | 0.0457 (16) | −0.0271 (18) | −0.0201 (18) |
| O7 | 0.0794 (15) | 0.0655 (14) | 0.122 (2) | −0.0015 (11) | −0.0130 (14) | −0.0100 (13) |
| N1 | 0.0480 (12) | 0.0551 (12) | 0.0622 (14) | 0.0009 (9) | −0.0043 (10) | 0.0008 (10) |
| N2 | 0.0546 (15) | 0.105 (2) | 0.0549 (14) | −0.0166 (15) | −0.0023 (11) | 0.0122 (14) |
| N3 | 0.0634 (15) | 0.0656 (15) | 0.093 (2) | 0.0088 (13) | −0.0045 (14) | 0.0049 (14) |
| C1 | 0.0465 (14) | 0.0586 (15) | 0.0560 (15) | 0.0011 (12) | 0.0016 (11) | 0.0001 (12) |
| C2 | 0.0458 (13) | 0.0576 (15) | 0.0452 (13) | 0.0029 (11) | 0.0045 (10) | 0.0006 (11) |
| C3 | 0.0506 (15) | 0.0693 (17) | 0.0544 (15) | 0.0061 (12) | 0.0004 (11) | 0.0038 (12) |
| C4 | 0.0638 (17) | 0.0657 (18) | 0.0753 (19) | 0.0196 (14) | −0.0021 (15) | 0.0069 (15) |
| C5 | 0.077 (2) | 0.0551 (17) | 0.094 (2) | 0.0141 (15) | −0.0024 (17) | −0.0024 (16) |
| C6 | 0.0644 (17) | 0.0556 (16) | 0.080 (2) | 0.0028 (13) | −0.0027 (14) | −0.0031 (14) |
| C7 | 0.0497 (14) | 0.0573 (15) | 0.0500 (14) | 0.0061 (11) | 0.0052 (11) | 0.0035 (11) |
| C8 | 0.0514 (15) | 0.0647 (17) | 0.0573 (15) | −0.0025 (12) | 0.0015 (12) | −0.0026 (13) |
| C9 | 0.0438 (13) | 0.0612 (16) | 0.0501 (14) | −0.0029 (11) | 0.0038 (11) | 0.0037 (12) |
| C10 | 0.0486 (14) | 0.0701 (17) | 0.0488 (14) | −0.0094 (12) | 0.0034 (11) | 0.0023 (12) |
| C11 | 0.0437 (14) | 0.085 (2) | 0.0463 (14) | −0.0120 (13) | 0.0009 (11) | 0.0105 (13) |
| C12 | 0.0464 (14) | 0.0742 (19) | 0.0664 (17) | 0.0013 (13) | 0.0016 (12) | 0.0177 (15) |
| C13 | 0.0488 (14) | 0.0588 (16) | 0.0682 (17) | −0.0017 (12) | 0.0053 (12) | 0.0104 (13) |
| C14 | 0.0458 (13) | 0.0598 (15) | 0.0565 (15) | −0.0060 (11) | −0.0001 (11) | 0.0051 (12) |
| C15 | 0.075 (2) | 0.0586 (18) | 0.121 (3) | −0.0012 (16) | −0.011 (2) | −0.0072 (18) |
| C16 | 0.086 (3) | 0.075 (3) | 0.243 (6) | −0.011 (2) | −0.036 (3) | −0.007 (3) |
| O1—C1 | 1.319 (3) | C5—C6 | 1.378 (4) |
| O1—C15 | 1.460 (4) | C5—H5 | 0.9300 |
| O2—C1 | 1.217 (3) | C6—C7 | 1.393 (4) |
| O3—C8 | 1.225 (3) | C6—H6 | 0.9300 |
| O4—N2 | 1.221 (4) | C8—C9 | 1.503 (4) |
| O5—N2 | 1.221 (4) | C9—C10 | 1.390 (4) |
| O6—N3 | 1.214 (3) | C9—C14 | 1.396 (4) |
| O7—N3 | 1.212 (3) | C10—C11 | 1.381 (4) |
| N1—C8 | 1.346 (3) | C10—H10 | 0.9300 |
| N1—C7 | 1.405 (3) | C11—C12 | 1.378 (4) |
| N1—H1 | 0.8600 | C12—C13 | 1.370 (4) |
| N2—C11 | 1.468 (3) | C12—H12 | 0.9300 |
| N3—C13 | 1.480 (4) | C13—C14 | 1.376 (4) |
| C1—C2 | 1.488 (4) | C14—H14 | 0.9300 |
| C2—C3 | 1.395 (3) | C15—C16 | 1.458 (5) |
| C2—C7 | 1.407 (4) | C15—H15A | 0.9700 |
| C3—C4 | 1.382 (4) | C15—H15B | 0.9700 |
| C3—H3 | 0.9300 | C16—H16A | 0.9600 |
| C4—C5 | 1.366 (4) | C16—H16B | 0.9600 |
| C4—H4 | 0.9300 | C16—H16C | 0.9600 |
| C1—O1—C15 | 117.0 (2) | O3—C8—C9 | 119.6 (2) |
| C8—N1—C7 | 129.4 (2) | N1—C8—C9 | 115.6 (2) |
| C8—N1—H1 | 115.3 | C10—C9—C14 | 119.1 (2) |
| C7—N1—H1 | 115.3 | C10—C9—C8 | 116.7 (2) |
| O5—N2—O4 | 123.3 (3) | C14—C9—C8 | 124.1 (2) |
| O5—N2—C11 | 117.9 (3) | C11—C10—C9 | 119.4 (3) |
| O4—N2—C11 | 118.7 (3) | C11—C10—H10 | 120.3 |
| O7—N3—O6 | 124.2 (3) | C9—C10—H10 | 120.3 |
| O7—N3—C13 | 118.0 (2) | C12—C11—C10 | 122.6 (2) |
| O6—N3—C13 | 117.8 (3) | C12—C11—N2 | 118.8 (3) |
| O2—C1—O1 | 122.5 (2) | C10—C11—N2 | 118.4 (3) |
| O2—C1—C2 | 125.2 (2) | C13—C12—C11 | 116.6 (3) |
| O1—C1—C2 | 112.3 (2) | C13—C12—H12 | 121.7 |
| C3—C2—C7 | 119.1 (2) | C11—C12—H12 | 121.7 |
| C3—C2—C1 | 119.4 (2) | C12—C13—C14 | 123.5 (3) |
| C7—C2—C1 | 121.5 (2) | C12—C13—N3 | 118.2 (2) |
| C4—C3—C2 | 121.0 (3) | C14—C13—N3 | 118.2 (2) |
| C4—C3—H3 | 119.5 | C13—C14—C9 | 118.8 (2) |
| C2—C3—H3 | 119.5 | C13—C14—H14 | 120.6 |
| C5—C4—C3 | 119.2 (3) | C9—C14—H14 | 120.6 |
| C5—C4—H4 | 120.4 | C16—C15—O1 | 107.6 (3) |
| C3—C4—H4 | 120.4 | C16—C15—H15A | 110.2 |
| C4—C5—C6 | 121.7 (3) | O1—C15—H15A | 110.2 |
| C4—C5—H5 | 119.2 | C16—C15—H15B | 110.2 |
| C6—C5—H5 | 119.2 | O1—C15—H15B | 110.2 |
| C5—C6—C7 | 119.9 (3) | H15A—C15—H15B | 108.5 |
| C5—C6—H6 | 120.0 | C15—C16—H16A | 109.5 |
| C7—C6—H6 | 120.0 | C15—C16—H16B | 109.5 |
| C6—C7—C2 | 119.1 (2) | H16A—C16—H16B | 109.5 |
| C6—C7—N1 | 122.3 (2) | C15—C16—H16C | 109.5 |
| C2—C7—N1 | 118.6 (2) | H16A—C16—H16C | 109.5 |
| O3—C8—N1 | 124.8 (3) | H16B—C16—H16C | 109.5 |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N1—H1···O2 | 0.86 | 1.92 | 2.641 (3) | 140. |
| C16—H16A···O3i | 0.96 | 2.55 | 3.402 (4) | 148 |
| Symmetry codes: (i) −x+1, y+1/2, −z+3/2. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N1—H1···O2 | 0.86 | 1.92 | 2.641 (3) | 140. |
| C16—H16A···O3i | 0.96 | 2.55 | 3.402 (4) | 148 |
| Symmetry codes: (i) −x+1, y+1/2, −z+3/2. |
Dr. Wesley T.K. Chan, Professor Z. Y. Zhou, and the Hong Kong Polytechnic University are sincerely thanked for helping to collect the X-Ray data.
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.
Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. 341, 555–1573.
Bruker (2007). APEX2 and SAINT, Bruker AXS Inc., Madison, Wisconsin, USA.
Gowda, B. T., Sowmya, B. P., Kožíšek, J., Tokarčík, M. & Fuess, H. (2007a). Acta Cryst. E63, o2906.
Gowda, B. T., Sowmya, B. P., Tokarčík, M., Kožíšek, J. & Fuess, H. (2007b). Acta Cryst. E63, o3326.
Gowda, B. T., Sowmya, B. P., Tokarčík, M., Kožíšek, J. & Fuess, H. (2007c). Acta Cryst. E63, o3365.
Karle, I. L. & Brockway, L. O. (1944). J. Am. Chem. Soc. 66, 1974–1979.
Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). Mercury. J. Appl. Cryst. 41, 466-470.
Saeed, S., Jasinski, J. P. & Butcher, R. J. (2011a). Acta Cryst. E67, o279.
Saeed, S., Rashid, N., Ng, S. W. & Tiekink, E. R. T. (2011b). Acta Cryst. E67, o1194.
Sheldrick, G. M. (2004). SADABS. University of Göttingen, Germany.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
In spite of the fact that the molecule is an extensively conjugated aromatic system, the molecule is not co-planar. This may be due to the steric hindrance between the ortho-H ··· amide H-atoms. The twisting away from coplanarity may help to relief this steric hindrance and results in an H14···H1 distance of 2.016 Å. This is in analogy to Karle and Brockway's suggestion that the steric hindrance between the ortho hydrogen atoms in biphenyl may be the reason for the non-coplanarity of the structure (Karle and Brockway, 1944). The dihedral angle between the two phenyl ring planes is about 17.4 (1)°. Both nitro groups are slightly twisted, 4.9 (2)° and 4.0 (2)° respectively, from the phenyl ring plane, C9—C11.
There is an intra-molecular N1—H1···O2 interaction. A weak intermolecular C16—H16A···O3(1 - x,1/2 + y,3/2 - z) hydrogen bond may help to align the molecules to endless chains along the b-axis in the crystal lattice. In addition, the conjugated ring planes of the title molecules are stacked along the c-axis with perpendicular distance between ring planes being 3.38 (1) Å.