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access4-(4-Nitrobenzyl)morpholine
aDepartment of Applied Chemistry, College of Chemical Engineering, Sichuan University, Chengdu 610041, People's Republic of China, bState Key Laboratory of Biotherapy and Cancer Center, West China Hospital, West China Medical School, Sichuan University, Chengdu 610041, People's Republic of China, and cWest China School of Pharmacy, Sichuan University, Chengdu 610041, People's Republic of China
*Correspondence e-mail: xieym@scu.edu.cn
In the title compound, C11H14N2O3, an intermolecular interaction between a nitro group O atom and a neighboring benzene ring helps to stabilize the [N⋯centroid = 3.933 (2) Å]. No classical hydrogen bonds are observed in the crystal packing.
Related literature
For the biological activity of 4-(4-nitrobenzyl)morpholine derivatives, see: Lan et al. (2010![[Lan, P., Chen, W. N., Xiao, G. K., Sun, P. H. & Chen, W. M. (2010). Bioorg. Med. Chem. Lett. 20, 6764-6772.]](../../../../../../logos/arrows/e_arr.gif "Lan, P., Chen, W. N., Xiao, G. K., Sun, P. H. & Chen, W. M. (2010). Bioorg. Med. Chem. Lett. 20, 6764-6772.")
); Bavetsias et al. (2010). For the synthesis, see: Tsou et al. (2008). For standard bond lengths, see: Allen et al. (1987).
![[Scheme 1]](vm2073scheme1.gif)
Experimental
Crystal data
|
Data collection: CrysAlis PRO (Oxford Diffraction, 2006); cell CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2.
Supporting information
contains datablocks I, global. DOI: 10.1107/S1600536811005964/vm2073sup1.cif
Structure factors: contains datablock I. DOI: 10.1107/S1600536811005964/vm2073Isup2.hkl
The title compound was prepared by a method similar to that of Tsou et al. (2008). Crystals suitable for X-ray analysis were obtained by slow evaporation from a solution of dichloromethane.
All H atoms were positioned geometrically (C—H = 0.93–0.97 Å, N–H =0.91 Å) and allowed to ride on their parent atoms, with Uiso(H) = 1.2Ueq(parent).
Data collection: CrysAlis PRO (Oxford Diffraction, 2006); cell CrysAlis PRO (Oxford Diffraction, 2006); data reduction: CrysAlis PRO (Oxford Diffraction, 2006); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).
![[Figure 1]](./vm2073fig1thm.gif) | Fig. 1. The molecular structure of the title compound with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. |
![[Figure 2]](./vm2073fig2thm.gif) | Fig. 2. Packing diagram of the title compound showing the intermolecular interaction (dashed lines) between nitro group atom O3 and benzene ring C1-C6 (centroid indicated by pink sphere). |
| C11H14N2O3 | F(000) = 472 |
| Mr = 222.24 | Dx = 1.330 Mg m−3 |
| Monoclinic, P21/c | Mo Kα radiation, λ = 0.7107 Å |
| Hall symbol: -P 2ybc | Cell parameters from 2399 reflections |
| a = 6.1371 (2) Å | θ = 3.1–29.2° |
| b = 8.2535 (4) Å | µ = 0.10 mm−1 |
| c = 21.9867 (9) Å | T = 293 K |
| β = 94.929 (3)° | Block, yellow |
| V = 1109.58 (8) Å3 | 0.40 × 0.30 × 0.25 mm |
| Z = 4 |
| Oxford Diffraction Xcalibur Eos diffractometer | 2264 independent reflections |
| Radiation source: fine-focus sealed tube | 1640 reflections with I > 2σ(I) |
| Graphite monochromator | Rint = 0.018 |
| Detector resolution: 16.0874 pixels mm-1 | θmax = 26.4°, θmin = 3.1° |
| ω scans | h = −7→7 |
| Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2006) | k = −8→10 |
| Tmin = 0.946, Tmax = 1.0 | l = −25→27 |
| 6059 measured reflections |
| 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)] = 0.044 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.106 | H-atom parameters constrained |
| S = 1.04 | w = 1/[σ2(Fo2) + (0.0423P)2 + 0.1325P] where P = (Fo2 + 2Fc2)/3 |
| 2264 reflections | (Δ/σ)max < 0.001 |
| 145 parameters | Δρmax = 0.12 e Å−3 |
| 0 restraints | Δρmin = −0.13 e Å−3 |
| C11H14N2O3 | V = 1109.58 (8) Å3 |
| Mr = 222.24 | Z = 4 |
| Monoclinic, P21/c | Mo Kα radiation |
| a = 6.1371 (2) Å | µ = 0.10 mm−1 |
| b = 8.2535 (4) Å | T = 293 K |
| c = 21.9867 (9) Å | 0.40 × 0.30 × 0.25 mm |
| β = 94.929 (3)° |
| Oxford Diffraction Xcalibur Eos diffractometer | 2264 independent reflections |
| Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2006) | 1640 reflections with I > 2σ(I) |
| Tmin = 0.946, Tmax = 1.0 | Rint = 0.018 |
| 6059 measured reflections |
| R[F2 > 2σ(F2)] = 0.044 | 0 restraints |
| wR(F2) = 0.106 | H-atom parameters constrained |
| S = 1.04 | Δρmax = 0.12 e Å−3 |
| 2264 reflections | Δρmin = −0.13 e Å−3 |
| 145 parameters |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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 | 0.40024 (19) | 0.31753 (14) | 0.53296 (5) | 0.0556 (3) | |
| O2 | −0.4376 (2) | −0.42771 (17) | 0.28701 (7) | 0.0751 (4) | |
| O3 | −0.1642 (2) | −0.57082 (16) | 0.32340 (8) | 0.0808 (5) | |
| N1 | 0.33645 (19) | 0.14840 (16) | 0.41946 (6) | 0.0417 (3) | |
| N2 | −0.2491 (2) | −0.44089 (19) | 0.30912 (6) | 0.0530 (4) | |
| C1 | −0.1173 (2) | −0.29260 (19) | 0.31894 (7) | 0.0413 (4) | |
| C2 | −0.2096 (2) | −0.1454 (2) | 0.30324 (7) | 0.0461 (4) | |
| H2 | −0.3521 | −0.1392 | 0.2853 | 0.055* | |
| C3 | −0.0870 (2) | −0.0064 (2) | 0.31460 (7) | 0.0467 (4) | |
| H3 | −0.1484 | 0.0941 | 0.3044 | 0.056* | |
| C4 | 0.1268 (2) | −0.0148 (2) | 0.34109 (7) | 0.0420 (4) | |
| C5 | 0.2166 (2) | −0.1668 (2) | 0.35492 (7) | 0.0468 (4) | |
| H5 | 0.3605 | −0.1743 | 0.3718 | 0.056* | |
| C6 | 0.0965 (3) | −0.3056 (2) | 0.34414 (7) | 0.0471 (4) | |
| H6 | 0.1576 | −0.4066 | 0.3536 | 0.057* | |
| C7 | 0.2629 (3) | 0.1353 (2) | 0.35452 (7) | 0.0493 (4) | |
| H7A | 0.3893 | 0.1325 | 0.3309 | 0.059* | |
| H7B | 0.1771 | 0.2302 | 0.3421 | 0.059* | |
| C8 | 0.5018 (2) | 0.2751 (2) | 0.43006 (8) | 0.0499 (4) | |
| H8B | 0.4409 | 0.3785 | 0.4162 | 0.060* | |
| H8A | 0.6256 | 0.2513 | 0.4069 | 0.060* | |
| C9 | 0.5767 (3) | 0.2851 (2) | 0.49693 (9) | 0.0550 (5) | |
| H9A | 0.6451 | 0.1835 | 0.5100 | 0.066* | |
| H9B | 0.6853 | 0.3701 | 0.5033 | 0.066* | |
| C10 | 0.1559 (2) | 0.1839 (2) | 0.45620 (8) | 0.0502 (4) | |
| H10A | 0.0466 | 0.0991 | 0.4507 | 0.060* | |
| H10B | 0.0879 | 0.2855 | 0.4430 | 0.060* | |
| C11 | 0.2381 (3) | 0.1952 (2) | 0.52265 (8) | 0.0566 (5) | |
| H11B | 0.1165 | 0.2191 | 0.5466 | 0.068* | |
| H11A | 0.2992 | 0.0916 | 0.5361 | 0.068* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| O1 | 0.0660 (7) | 0.0481 (7) | 0.0523 (7) | −0.0032 (6) | 0.0017 (6) | −0.0124 (6) |
| O2 | 0.0609 (8) | 0.0800 (10) | 0.0819 (10) | −0.0136 (7) | −0.0089 (7) | −0.0130 (8) |
| O3 | 0.0861 (10) | 0.0489 (9) | 0.1079 (12) | −0.0023 (7) | 0.0107 (8) | 0.0089 (8) |
| N1 | 0.0422 (7) | 0.0462 (8) | 0.0372 (7) | −0.0052 (6) | 0.0053 (5) | −0.0017 (6) |
| N2 | 0.0584 (9) | 0.0565 (10) | 0.0451 (8) | −0.0045 (7) | 0.0101 (7) | −0.0050 (7) |
| C1 | 0.0460 (9) | 0.0465 (10) | 0.0314 (8) | 0.0000 (7) | 0.0045 (6) | −0.0033 (7) |
| C2 | 0.0416 (8) | 0.0573 (11) | 0.0385 (9) | 0.0041 (7) | −0.0026 (7) | −0.0006 (8) |
| C3 | 0.0516 (9) | 0.0469 (10) | 0.0408 (9) | 0.0081 (7) | −0.0002 (7) | 0.0019 (7) |
| C4 | 0.0474 (9) | 0.0495 (10) | 0.0294 (8) | 0.0016 (7) | 0.0055 (6) | −0.0017 (7) |
| C5 | 0.0399 (8) | 0.0607 (12) | 0.0394 (9) | 0.0034 (8) | −0.0001 (7) | −0.0014 (8) |
| C6 | 0.0502 (9) | 0.0476 (10) | 0.0435 (9) | 0.0104 (7) | 0.0044 (7) | 0.0016 (8) |
| C7 | 0.0542 (9) | 0.0555 (11) | 0.0386 (9) | −0.0047 (8) | 0.0065 (7) | 0.0027 (8) |
| C8 | 0.0463 (9) | 0.0492 (11) | 0.0546 (11) | −0.0072 (7) | 0.0059 (7) | 0.0007 (8) |
| C9 | 0.0523 (10) | 0.0501 (11) | 0.0610 (12) | −0.0059 (8) | −0.0047 (8) | −0.0050 (9) |
| C10 | 0.0457 (9) | 0.0588 (11) | 0.0468 (10) | −0.0069 (7) | 0.0080 (7) | −0.0067 (8) |
| C11 | 0.0632 (11) | 0.0609 (12) | 0.0472 (10) | −0.0092 (9) | 0.0128 (8) | −0.0105 (9) |
| O1—C9 | 1.421 (2) | C5—H5 | 0.9300 |
| O1—C11 | 1.4218 (19) | C5—C6 | 1.372 (2) |
| O2—N2 | 1.2210 (17) | C6—H6 | 0.9300 |
| O3—N2 | 1.2214 (17) | C7—H7A | 0.9700 |
| N1—C7 | 1.4641 (19) | C7—H7B | 0.9700 |
| N1—C8 | 1.4616 (19) | C8—H8B | 0.9700 |
| N1—C10 | 1.456 (2) | C8—H8A | 0.9700 |
| N2—C1 | 1.473 (2) | C8—C9 | 1.504 (2) |
| C1—C2 | 1.372 (2) | C9—H9A | 0.9700 |
| C1—C6 | 1.384 (2) | C9—H9B | 0.9700 |
| C2—H2 | 0.9300 | C10—H10A | 0.9700 |
| C2—C3 | 1.383 (2) | C10—H10B | 0.9700 |
| C3—H3 | 0.9300 | C10—C11 | 1.507 (2) |
| C3—C4 | 1.3911 (19) | C11—H11B | 0.9700 |
| C4—C5 | 1.393 (2) | C11—H11A | 0.9700 |
| C4—C7 | 1.509 (2) | ||
| O1—C9—C8 | 111.83 (13) | C4—C3—H3 | 119.6 |
| O1—C9—H9A | 109.3 | C4—C5—H5 | 119.4 |
| O1—C9—H9B | 109.3 | C4—C7—H7A | 109.3 |
| O1—C11—C10 | 111.71 (14) | C4—C7—H7B | 109.3 |
| O1—C11—H11B | 109.3 | C5—C4—C7 | 119.67 (13) |
| O1—C11—H11A | 109.3 | C5—C6—C1 | 118.75 (15) |
| O2—N2—O3 | 123.32 (15) | C5—C6—H6 | 120.6 |
| O2—N2—C1 | 118.31 (15) | C6—C1—N2 | 118.95 (15) |
| O3—N2—C1 | 118.38 (14) | C6—C5—C4 | 121.20 (14) |
| N1—C7—C4 | 111.73 (13) | C6—C5—H5 | 119.4 |
| N1—C7—H7A | 109.3 | H7A—C7—H7B | 107.9 |
| N1—C7—H7B | 109.3 | C8—N1—C7 | 111.09 (12) |
| N1—C8—H8B | 109.6 | C8—C9—H9A | 109.3 |
| N1—C8—H8A | 109.6 | C8—C9—H9B | 109.3 |
| N1—C8—C9 | 110.15 (14) | H8B—C8—H8A | 108.1 |
| N1—C10—H10A | 109.6 | C9—O1—C11 | 109.49 (13) |
| N1—C10—H10B | 109.6 | C9—C8—H8B | 109.6 |
| N1—C10—C11 | 110.07 (13) | C9—C8—H8A | 109.6 |
| C1—C2—H2 | 120.6 | H9A—C9—H9B | 107.9 |
| C1—C2—C3 | 118.87 (14) | C10—N1—C7 | 111.73 (12) |
| C1—C6—H6 | 120.6 | C10—N1—C8 | 108.57 (13) |
| C2—C1—N2 | 119.30 (14) | C10—C11—H11B | 109.3 |
| C2—C1—C6 | 121.76 (15) | C10—C11—H11A | 109.3 |
| C2—C3—H3 | 119.6 | H10A—C10—H10B | 108.2 |
| C2—C3—C4 | 120.88 (15) | C11—C10—H10A | 109.6 |
| C3—C2—H2 | 120.6 | C11—C10—H10B | 109.6 |
| C3—C4—C5 | 118.51 (15) | H11B—C11—H11A | 107.9 |
| C3—C4—C7 | 121.81 (15) |
Experimental details
| Crystal data | |
| Chemical formula | C11H14N2O3 |
| Mr | 222.24 |
| Crystal system, space group | Monoclinic, P21/c |
| Temperature (K) | 293 |
| a, b, c (Å) | 6.1371 (2), 8.2535 (4), 21.9867 (9) |
| β (°) | 94.929 (3) |
| V (Å3) | 1109.58 (8) |
| Z | 4 |
| Radiation type | Mo Kα |
| µ (mm−1) | 0.10 |
| Crystal size (mm) | 0.40 × 0.30 × 0.25 |
| Data collection | |
| Diffractometer | Oxford Diffraction Xcalibur Eos diffractometer |
| Absorption correction | Multi-scan (CrysAlis PRO; Oxford Diffraction, 2006) |
| Tmin, Tmax | 0.946, 1.0 |
| No. of measured, independent and observed [I > 2σ(I)] reflections | 6059, 2264, 1640 |
| Rint | 0.018 |
| (sin θ/λ)max (Å−1) | 0.625 |
| Refinement | |
| R[F2 > 2σ(F2)], wR(F2), S | 0.044, 0.106, 1.04 |
| No. of reflections | 2264 |
| No. of parameters | 145 |
| H-atom treatment | H-atom parameters constrained |
| Δρmax, Δρmin (e Å−3) | 0.12, −0.13 |
Computer programs: CrysAlis PRO (Oxford Diffraction, 2006), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), OLEX2 (Dolomanov et al., 2009).
Acknowledgements
We thank the Analytical and Testing Center of Sichuan University for the X-ray measurements.
References
Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. 1–19. CrossRef Web of Science Google Scholar
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| CRYSTALLOGRAPHIC COMMUNICATIONS |
4-(4-nitrobenzyl)morpholine derivatives are of great importance owing to their anticancer activity (Lan et al., 2010; Bavetsias et al., 2010). The title compound is one of the key intermediates in our synthetic investigations of anticancer drugs. In this paper, we synthesized the title compound and report its crystal structure. In the title compound, C11H14N2O3, (Fig. 1), the bond lengths and angles are within normal ranges (Allen et al., 1987). The dihedral angle between the best planes between the phenyl and morpholino rings is 87.78 (10)°. An intermolecular interaction between the nitro group atom O3 and the benzene ring helps to stabilize the crystal structure. The distance O3···Cg(1)a is 3.647 (2) Å (Fig.2, Cg(1) is the centroid of benzene ring C1-C6, symmetry operation (a): -x, -1/2+y, 1/2-z). There are no classical hydrogen bonds observed in the crystal packing.