Acta Cryst. (2012). E68, o3098 [ doi:10.1107/S1600536812040895 ]
In the title compound, C13H15N3O7, the dihedral angle between the amide plane (r.m.s. deviation = 0.008 Å) and the benzene ring is 33.2 (2)°. In the crystal, molecules are connected by N-H
O=C hydrogen bonds, forming a chain along the b-axis direction.
To a solution of methyl 2-amino-3-methylbutanoate hydrochloride (0.8 g, 5 mmol) and triethylamine (0.5 mL) in dry methylene chloride (100 mL) was added to 3,5-dinitrobenzoyl chloride (1.1 g, 5 mmol)in dry methylene chloride (50 mL) at 273 K. The mixture was allowed to warm to room temperature for 0.5 h. After concentrating, the residue was subjected to chromatography(petroleum ether/ acetone, 4:1) to provide the product as a white crystal (1.2 g, 71.1%).
The C-bound H-atoms were included in calculated positions and treated as riding atoms: C—H = 0.93, 0.96 and 0.98 Å for CH(aromatic), CH3 and CH(methine) H-atoms, respectively,and N—H =0.86 Å, with Uiso(H)= k τimes Ueq(parent C-atom, N), where k = 1.5 for CH3 H-atoms and k = 1.2 for all other H-atoms. The absolute configuration can be assigned to be R according to the known chirality of the precursor, only.
Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: publCIF (Westrip, 2010).
![[Figure 1]](./kp2434fig1thm.gif)
| Fig. 1. A view of the molecular strcuture of the title compound; the displacement ellipsoids drawn at the 30% probability level. |
![[Figure 2]](./kp2434fig2thm.gif)
| Fig. 2. A view of the hydrogen bonded chain running in the [100] direction. The hydrogen bonds are shown as dashed lines. |
| C13H15N3O7 | F(000) = 680 |
| Mr = 325.28 | Dx = 1.394 Mg m−3 |
| Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: P 2ac 2ab | Cell parameters from 9233 reflections |
| a = 7.060 (2) Å | θ = 1.0–22.7° |
| b = 9.412 (3) Å | µ = 0.12 mm−1 |
| c = 23.321 (6) Å | T = 296 K |
| V = 1549.8 (7) Å3 | Block, colourless |
| Z = 4 | 0.43 × 0.32 × 0.30 mm |
| Bruker APEXII CCD area-detector diffractometer | 3580 independent reflections |
| Radiation source: fine-focus sealed tube | 3003 reflections with I > 2σ(I) |
| Graphite monochromator | Rint = 0.023 |
| phi and ω scans | θmax = 27.7°, θmin = 1.8° |
| Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −7→9 |
| Tmin = 0.660, Tmax = 0.746 | k = −12→12 |
| 9197 measured reflections | l = −26→30 |
| 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)] = 0.045 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.131 | H-atom parameters constrained |
| S = 1.03 | w = 1/[σ2(Fo2) + (0.0802P)2 + 0.1123P] where P = (Fo2 + 2Fc2)/3 |
| 3580 reflections | (Δ/σ)max < 0.001 |
| 208 parameters | Δρmax = 0.20 e Å−3 |
| 0 restraints | Δρmin = −0.18 e Å−3 |
| C13H15N3O7 | V = 1549.8 (7) Å3 |
| Mr = 325.28 | Z = 4 |
| Orthorhombic, P212121 | Mo Kα radiation |
| a = 7.060 (2) Å | µ = 0.12 mm−1 |
| b = 9.412 (3) Å | T = 296 K |
| c = 23.321 (6) Å | 0.43 × 0.32 × 0.30 mm |
| Bruker APEXII CCD area-detector diffractometer | 3580 independent reflections |
| Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 3003 reflections with I > 2σ(I) |
| Tmin = 0.660, Tmax = 0.746 | Rint = 0.023 |
| 9197 measured reflections | θmax = 27.7° |
| R[F2 > 2σ(F2)] = 0.045 | H-atom parameters constrained |
| wR(F2) = 0.131 | Δρmax = 0.20 e Å−3 |
| S = 1.03 | Δρmin = −0.18 e Å−3 |
| 3580 reflections | Absolute structure: ? |
| 208 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. C10, C11, C13 and C12 belong to terminal alkyl chains which show signs of disorder and have higher thermal parameters. |
| x | y | z | Uiso*/Ueq | ||
| C1 | 1.2857 (3) | 0.28856 (19) | 0.10037 (8) | 0.0526 (4) | |
| C2 | 1.2504 (3) | 0.23672 (19) | 0.15455 (8) | 0.0503 (4) | |
| H2A | 1.3390 | 0.1801 | 0.1732 | 0.060* | |
| C3 | 1.0795 (2) | 0.27084 (17) | 0.18071 (7) | 0.0453 (4) | |
| C4 | 0.9487 (3) | 0.35376 (18) | 0.15216 (8) | 0.0469 (4) | |
| H4A | 0.8350 | 0.3785 | 0.1696 | 0.056* | |
| C5 | 0.9895 (3) | 0.39948 (18) | 0.09717 (7) | 0.0495 (4) | |
| C6 | 1.1576 (3) | 0.3692 (2) | 0.07014 (8) | 0.0521 (4) | |
| H6A | 1.1834 | 0.4015 | 0.0333 | 0.062* | |
| C7 | 1.0425 (2) | 0.21140 (17) | 0.23943 (7) | 0.0460 (4) | |
| C8 | 0.8869 (3) | 0.2398 (2) | 0.33103 (8) | 0.0557 (4) | |
| H8A | 0.9465 | 0.1466 | 0.3358 | 0.067* | |
| C9 | 0.9790 (4) | 0.3399 (3) | 0.37526 (9) | 0.0671 (6) | |
| C10 | 0.5694 (5) | 0.3567 (4) | 0.3394 (2) | 0.1160 (12) | |
| H15A | 0.4365 | 0.3390 | 0.3442 | 0.174* | |
| H15B | 0.5902 | 0.4049 | 0.3036 | 0.174* | |
| H15C | 0.6142 | 0.4149 | 0.3703 | 0.174* | |
| C11 | 0.5992 (4) | 0.1150 (4) | 0.29434 (14) | 0.0947 (9) | |
| H14A | 0.4656 | 0.1019 | 0.2998 | 0.142* | |
| H14B | 0.6627 | 0.0253 | 0.2983 | 0.142* | |
| H14C | 0.6221 | 0.1526 | 0.2567 | 0.142* | |
| C12 | 1.0720 (6) | 0.3594 (4) | 0.47134 (13) | 0.1166 (13) | |
| H12A | 1.0668 | 0.3069 | 0.5066 | 0.175* | |
| H12B | 1.0072 | 0.4483 | 0.4760 | 0.175* | |
| H12C | 1.2018 | 0.3769 | 0.4613 | 0.175* | |
| C13 | 0.6744 (4) | 0.2186 (3) | 0.33924 (11) | 0.0735 (6) | |
| H13A | 0.6560 | 0.1746 | 0.3769 | 0.088* | |
| N1 | 1.4675 (3) | 0.2555 (2) | 0.07277 (9) | 0.0671 (5) | |
| N2 | 0.8475 (3) | 0.48375 (18) | 0.06597 (7) | 0.0613 (4) | |
| N5 | 0.9379 (2) | 0.29050 (15) | 0.27435 (6) | 0.0506 (4) | |
| H5A | 0.9000 | 0.3728 | 0.2632 | 0.061* | |
| O1 | 1.5804 (3) | 0.1847 (3) | 0.09906 (10) | 0.0990 (6) | |
| O2 | 1.4962 (3) | 0.3026 (2) | 0.02520 (8) | 0.0877 (6) | |
| O3 | 0.8739 (3) | 0.5050 (2) | 0.01510 (7) | 0.0856 (5) | |
| O4 | 0.7125 (3) | 0.5274 (2) | 0.09269 (7) | 0.0781 (5) | |
| O5 | 1.1072 (2) | 0.09485 (13) | 0.25244 (6) | 0.0596 (4) | |
| O6 | 0.9809 (3) | 0.2774 (2) | 0.42582 (6) | 0.0897 (6) | |
| O7 | 1.0395 (5) | 0.4534 (3) | 0.36573 (10) | 0.1163 (9) |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| C1 | 0.0540 (10) | 0.0489 (9) | 0.0547 (10) | −0.0103 (8) | 0.0075 (8) | −0.0126 (8) |
| C2 | 0.0526 (9) | 0.0426 (8) | 0.0556 (10) | −0.0011 (7) | −0.0013 (8) | −0.0040 (7) |
| C3 | 0.0525 (9) | 0.0375 (7) | 0.0460 (8) | −0.0054 (7) | −0.0006 (7) | −0.0030 (7) |
| C4 | 0.0503 (9) | 0.0439 (8) | 0.0464 (8) | −0.0035 (7) | −0.0001 (7) | −0.0047 (7) |
| C5 | 0.0614 (10) | 0.0427 (8) | 0.0445 (8) | −0.0027 (8) | −0.0047 (8) | −0.0028 (7) |
| C6 | 0.0639 (11) | 0.0497 (9) | 0.0426 (8) | −0.0102 (8) | 0.0046 (8) | −0.0043 (7) |
| C7 | 0.0500 (9) | 0.0402 (8) | 0.0477 (8) | −0.0039 (7) | −0.0024 (7) | 0.0004 (7) |
| C8 | 0.0658 (11) | 0.0549 (10) | 0.0463 (9) | 0.0091 (9) | 0.0023 (8) | 0.0045 (8) |
| C9 | 0.0770 (14) | 0.0720 (13) | 0.0523 (11) | 0.0169 (12) | −0.0047 (10) | −0.0061 (9) |
| C10 | 0.0821 (19) | 0.094 (2) | 0.172 (4) | 0.0177 (17) | 0.034 (2) | 0.017 (2) |
| C11 | 0.0834 (18) | 0.099 (2) | 0.102 (2) | −0.0206 (17) | −0.0107 (15) | 0.0137 (17) |
| C12 | 0.152 (3) | 0.130 (3) | 0.0680 (16) | 0.019 (3) | −0.0295 (19) | −0.0348 (17) |
| C13 | 0.0736 (14) | 0.0762 (14) | 0.0707 (13) | −0.0033 (12) | 0.0113 (11) | 0.0167 (11) |
| N1 | 0.0613 (10) | 0.0632 (10) | 0.0769 (12) | −0.0070 (9) | 0.0174 (9) | −0.0107 (9) |
| N2 | 0.0743 (11) | 0.0594 (9) | 0.0504 (9) | 0.0028 (9) | −0.0069 (8) | 0.0018 (7) |
| N5 | 0.0629 (9) | 0.0432 (7) | 0.0456 (7) | 0.0071 (7) | 0.0047 (6) | 0.0055 (6) |
| O1 | 0.0641 (10) | 0.1110 (14) | 0.1218 (16) | 0.0183 (11) | 0.0206 (10) | 0.0107 (13) |
| O2 | 0.0948 (13) | 0.0910 (12) | 0.0773 (11) | −0.0046 (11) | 0.0372 (10) | −0.0117 (9) |
| O3 | 0.1103 (15) | 0.0954 (12) | 0.0511 (8) | 0.0146 (12) | −0.0049 (9) | 0.0146 (8) |
| O4 | 0.0800 (11) | 0.0881 (11) | 0.0661 (9) | 0.0258 (9) | −0.0040 (8) | 0.0041 (8) |
| O5 | 0.0776 (9) | 0.0431 (6) | 0.0580 (7) | 0.0098 (6) | 0.0016 (7) | 0.0035 (6) |
| O6 | 0.1274 (15) | 0.0904 (11) | 0.0512 (8) | 0.0167 (12) | −0.0109 (9) | −0.0112 (8) |
| O7 | 0.162 (2) | 0.0923 (13) | 0.0946 (14) | −0.0369 (15) | −0.0343 (14) | −0.0015 (12) |
| C1—C6 | 1.375 (3) | C9—O6 | 1.318 (3) |
| C1—C2 | 1.377 (3) | C10—C13 | 1.497 (4) |
| C1—N1 | 1.469 (3) | C10—H15A | 0.9600 |
| C2—C3 | 1.390 (3) | C10—H15B | 0.9600 |
| C2—H2A | 0.9300 | C10—H15C | 0.9600 |
| C3—C4 | 1.380 (3) | C11—C13 | 1.526 (4) |
| C3—C7 | 1.502 (2) | C11—H14A | 0.9600 |
| C4—C5 | 1.383 (3) | C11—H14B | 0.9600 |
| C4—H4A | 0.9300 | C11—H14C | 0.9600 |
| C5—C6 | 1.373 (3) | C12—O6 | 1.462 (3) |
| C5—N2 | 1.471 (3) | C12—H12A | 0.9600 |
| C6—H6A | 0.9300 | C12—H12B | 0.9600 |
| C7—O5 | 1.226 (2) | C12—H12C | 0.9600 |
| C7—N5 | 1.328 (2) | C13—H13A | 0.9800 |
| C8—N5 | 1.451 (2) | N1—O1 | 1.206 (3) |
| C8—C13 | 1.525 (3) | N1—O2 | 1.212 (3) |
| C8—C9 | 1.541 (3) | N2—O4 | 1.211 (2) |
| C8—H8A | 0.9800 | N2—O3 | 1.217 (2) |
| C9—O7 | 1.171 (3) | N5—H5A | 0.8600 |
| C6—C1—C2 | 123.15 (18) | H15A—C10—H15B | 109.5 |
| C6—C1—N1 | 117.83 (18) | C13—C10—H15C | 109.5 |
| C2—C1—N1 | 119.02 (19) | H15A—C10—H15C | 109.5 |
| C1—C2—C3 | 118.55 (18) | H15B—C10—H15C | 109.5 |
| C1—C2—H2A | 120.7 | C13—C11—H14A | 109.5 |
| C3—C2—H2A | 120.7 | C13—C11—H14B | 109.5 |
| C4—C3—C2 | 119.99 (17) | H14A—C11—H14B | 109.5 |
| C4—C3—C7 | 122.29 (16) | C13—C11—H14C | 109.5 |
| C2—C3—C7 | 117.70 (16) | H14A—C11—H14C | 109.5 |
| C3—C4—C5 | 118.94 (17) | H14B—C11—H14C | 109.5 |
| C3—C4—H4A | 120.5 | O6—C12—H12A | 109.5 |
| C5—C4—H4A | 120.5 | O6—C12—H12B | 109.5 |
| C6—C5—C4 | 122.75 (17) | H12A—C12—H12B | 109.5 |
| C6—C5—N2 | 118.28 (16) | O6—C12—H12C | 109.5 |
| C4—C5—N2 | 118.97 (17) | H12A—C12—H12C | 109.5 |
| C5—C6—C1 | 116.59 (17) | H12B—C12—H12C | 109.5 |
| C5—C6—H6A | 121.7 | C10—C13—C8 | 111.9 (2) |
| C1—C6—H6A | 121.7 | C10—C13—C11 | 112.6 (3) |
| O5—C7—N5 | 123.84 (16) | C8—C13—C11 | 109.9 (2) |
| O5—C7—C3 | 119.61 (16) | C10—C13—H13A | 107.4 |
| N5—C7—C3 | 116.54 (14) | C8—C13—H13A | 107.4 |
| N5—C8—C13 | 113.70 (18) | C11—C13—H13A | 107.4 |
| N5—C8—C9 | 107.70 (17) | O1—N1—O2 | 123.8 (2) |
| C13—C8—C9 | 114.29 (18) | O1—N1—C1 | 118.12 (19) |
| N5—C8—H8A | 106.9 | O2—N1—C1 | 118.0 (2) |
| C13—C8—H8A | 106.9 | O4—N2—O3 | 124.5 (2) |
| C9—C8—H8A | 106.9 | O4—N2—C5 | 117.71 (17) |
| O7—C9—O6 | 125.0 (2) | O3—N2—C5 | 117.81 (19) |
| O7—C9—C8 | 125.7 (2) | C7—N5—C8 | 120.85 (15) |
| O6—C9—C8 | 109.3 (2) | C7—N5—H5A | 119.6 |
| C13—C10—H15A | 109.5 | C8—N5—H5A | 119.6 |
| C13—C10—H15B | 109.5 | C9—O6—C12 | 114.7 (3) |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N5—H5A···O5i | 0.86 | 2.12 | 2.949 (2) | 161 |
| Symmetry code: (i) −x+2, y+1/2, −z+1/2. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N5—H5A···O5i | 0.86 | 2.12 | 2.949 (2) | 161.2 |
| Symmetry code: (i) −x+2, y+1/2, −z+1/2. |
The author thanks North China University of Water Source and Electric Power for supporting this study.
Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Sykes, B. M., Atwell, G. J., Hogg, A., Wilson, W. R., O'Connor, C. J. & Denny, W. A. (1999). J. Med. Chem. 42, 346–355.
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925.
Nitro and ester groups widely exist in variety of biologically active compounds that could be used as prodrugs (Sykes et al., 1999). We synthesized the title compound and determined its crystal structure (Fig. 1) whereas its biological activily is planned to be examined as well. In the crystal of the title compound, the carbonyl group acts as an acceptor and the amide group is a proton donor in the intermolecular N–H···O=C hydrogen bond, forming a chain along the b axis (Table 1, Fig. 2).