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accessN-(4-Chlorophenyl)-7-oxabicyclo[2.2.1]hept-5-ene-2,3-dicarboximide
aDepartment of Chemistry and Chemical Engineering, Weifang University, Weifang 261061, People's Republic of China
*Correspondence e-mail: ljwfu@163.com
In the title C14H10ClNO3, which contains four stereogenic centres, the cyclohexane ring tends towards a boat conformation, while the tetrahydrofuran and dihydrofuran rings adopt envelope conformations. The dihedral angle between the mean planes of the pyrrolidine-2,5-dione unit and the 4-chlorophenyl ring is 49.0 (2)°.
Related literature
For the biological activity of 7-oxa-bicyclo[2,2,1]hept-5-ene-2,3-dicarboxylic anhydride, see: Deng & Hu (2007![[Deng, L. P. & Hu, Y. Z. (2007). J. Heterocycl. Chem. 44, 597-601.]](../../../../../../logos/arrows/e_arr.gif "Deng, L. P. & Hu, Y. Z. (2007). J. Heterocycl. Chem. 44, 597-601.")
). For related structures, see: Goh et al. (2008); Hart et al. (2004).
![[Scheme 1]](is2633scheme1.gif)
Experimental
Crystal data
|
Data collection: SMART (Bruker, 1997); cell SAINT (Bruker, 1997); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.
Supporting information
contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536810047537/is2633sup1.cif
Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810047537/is2633Isup2.hkl
A mixture of exo-7-oxa-bicyclo[2,2,1]hept-5-ene-2,3-dicarboxylic anhydride (0.332 g, 2 mmol) and p-chloroaniline (0.255 g, 2 mmol) in methanol (5 ml) was stirred for 5 h at room temperature, and then refluxed for 1 h. After cooling, the precipitate was filtered and dried. The crude product of 20 mg was dissolved in methanol of 10 ml. The solution was filtered to remove impurities, and then the filtrate was left for crystallization at room temperature. Single-crystals suitable for X-ray diffraction were obtained by evaporation from the methanol solution after 5 d.
H atoms were initially located from difference maps and then refined in a riding model, with C—H = 0.93 or 0.98 Å and Uiso(H) = 1.2Ueq(C).
7-Oxa-bicyclo[2,2,1]hept-5-ene-2,3-dicarboxylic anhydride has been widely employed in clinical practice, as it is less toxic and much easier to be synthesized (Deng & Hu, 2007). Its derivatives are also pharmacologically active (Hart et al., 2004). In this paper, the structure of the title compound, (I), is reported (Fig. 1). The bond lengths and angles are as expected and comparable to those in the similar compounds (Goh et al., 2008). The dihedral angle between the pyrrolidine-2,5-dione plane and 4-chlorophenyl plane is 49.0 (2)°.
For the biological activity of 7-oxa-bicyclo[2,2,1]hept-5-ene-2,3-dicarboxylic anhydride, see: Deng & Hu (2007). For related structures, see: Goh et al. (2008); Hart et al. (2004).
Data collection: SMART (Bruker, 1997); cell SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
![[Figure 1]](./is2633fig1thm.gif) | Fig. 1. The molecular structure of (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at 30% probability level. |
| C14H10ClNO3 | F(000) = 568 |
| Mr = 275.68 | Dx = 1.495 Mg m−3 |
| Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -P 2ybc | Cell parameters from 1615 reflections |
| a = 10.4946 (11) Å | θ = 2.9–24.8° |
| b = 8.2890 (8) Å | µ = 0.31 mm−1 |
| c = 14.0871 (13) Å | T = 298 K |
| β = 91.538 (1)° | Block, light yellow |
| V = 1225.0 (2) Å3 | 0.40 × 0.33 × 0.21 mm |
| Z = 4 |
| Bruker SMART CCD area-detector diffractometer | 2156 independent reflections |
| Radiation source: fine-focus sealed tube | 1466 reflections with I > 2σ(I) |
| Graphite monochromator | Rint = 0.040 |
| φ and ω scans | θmax = 25.0°, θmin = 1.9° |
| Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −12→12 |
| Tmin = 0.885, Tmax = 0.937 | k = −9→9 |
| 5907 measured reflections | l = −13→16 |
| 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)] = 0.043 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.113 | H-atom parameters constrained |
| S = 1.07 | w = 1/[σ2(Fo2) + (0.0446P)2 + 0.4264P] where P = (Fo2 + 2Fc2)/3 |
| 2156 reflections | (Δ/σ)max < 0.001 |
| 172 parameters | Δρmax = 0.25 e Å−3 |
| 0 restraints | Δρmin = −0.33 e Å−3 |
| C14H10ClNO3 | V = 1225.0 (2) Å3 |
| Mr = 275.68 | Z = 4 |
| Monoclinic, P21/c | Mo Kα radiation |
| a = 10.4946 (11) Å | µ = 0.31 mm−1 |
| b = 8.2890 (8) Å | T = 298 K |
| c = 14.0871 (13) Å | 0.40 × 0.33 × 0.21 mm |
| β = 91.538 (1)° |
| Bruker SMART CCD area-detector diffractometer | 2156 independent reflections |
| Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1466 reflections with I > 2σ(I) |
| Tmin = 0.885, Tmax = 0.937 | Rint = 0.040 |
| 5907 measured reflections |
| R[F2 > 2σ(F2)] = 0.043 | 0 restraints |
| wR(F2) = 0.113 | H-atom parameters constrained |
| S = 1.07 | Δρmax = 0.25 e Å−3 |
| 2156 reflections | Δρmin = −0.33 e Å−3 |
| 172 parameters |
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 | ||
| Cl1 | 1.06821 (7) | 0.52842 (11) | 0.16059 (6) | 0.0601 (3) | |
| N1 | 0.58629 (19) | 0.2856 (3) | 0.31440 (13) | 0.0349 (5) | |
| O1 | 0.66611 (17) | 0.1666 (3) | 0.45091 (12) | 0.0482 (5) | |
| O2 | 0.45183 (18) | 0.3870 (3) | 0.19755 (13) | 0.0556 (6) | |
| O3 | 0.37280 (17) | 0.4471 (2) | 0.44140 (13) | 0.0444 (5) | |
| C1 | 0.5766 (3) | 0.2056 (3) | 0.40149 (18) | 0.0369 (6) | |
| C2 | 0.4383 (2) | 0.1821 (3) | 0.42057 (17) | 0.0361 (6) | |
| H2 | 0.4176 | 0.0697 | 0.4354 | 0.043* | |
| C3 | 0.3661 (2) | 0.2439 (3) | 0.33183 (17) | 0.0353 (6) | |
| H3 | 0.3157 | 0.1598 | 0.2994 | 0.042* | |
| C4 | 0.4678 (2) | 0.3141 (3) | 0.27085 (18) | 0.0369 (6) | |
| C5 | 0.7041 (2) | 0.3409 (3) | 0.27702 (17) | 0.0325 (6) | |
| C6 | 0.7316 (2) | 0.3134 (3) | 0.18301 (17) | 0.0377 (7) | |
| H6 | 0.6748 | 0.2558 | 0.1442 | 0.045* | |
| C7 | 0.8436 (2) | 0.3715 (3) | 0.14685 (18) | 0.0397 (7) | |
| H7 | 0.8623 | 0.3545 | 0.0835 | 0.048* | |
| C8 | 0.9268 (2) | 0.4544 (3) | 0.2053 (2) | 0.0407 (7) | |
| C9 | 0.9002 (2) | 0.4827 (3) | 0.2991 (2) | 0.0432 (7) | |
| H9 | 0.9575 | 0.5398 | 0.3377 | 0.052* | |
| C10 | 0.7882 (2) | 0.4258 (3) | 0.33505 (18) | 0.0381 (7) | |
| H10 | 0.7692 | 0.4445 | 0.3982 | 0.046* | |
| C11 | 0.3888 (3) | 0.3030 (4) | 0.49633 (18) | 0.0427 (7) | |
| H11 | 0.4427 | 0.3138 | 0.5539 | 0.051* | |
| C12 | 0.2531 (3) | 0.2520 (4) | 0.5124 (2) | 0.0519 (8) | |
| H12 | 0.2220 | 0.1981 | 0.5648 | 0.062* | |
| C13 | 0.1885 (3) | 0.3001 (4) | 0.4365 (2) | 0.0501 (8) | |
| H13 | 0.1015 | 0.2875 | 0.4243 | 0.060* | |
| C14 | 0.2830 (2) | 0.3796 (3) | 0.37332 (19) | 0.0432 (7) | |
| H14 | 0.2469 | 0.4559 | 0.3268 | 0.052* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Cl1 | 0.0375 (4) | 0.0665 (6) | 0.0769 (6) | −0.0031 (4) | 0.0100 (4) | 0.0018 (4) |
| N1 | 0.0347 (12) | 0.0361 (14) | 0.0336 (12) | −0.0010 (10) | −0.0036 (9) | 0.0051 (10) |
| O1 | 0.0459 (12) | 0.0553 (14) | 0.0429 (11) | 0.0061 (10) | −0.0086 (9) | 0.0132 (10) |
| O2 | 0.0503 (12) | 0.0730 (16) | 0.0430 (12) | 0.0006 (11) | −0.0072 (9) | 0.0236 (11) |
| O3 | 0.0454 (11) | 0.0324 (11) | 0.0551 (12) | −0.0050 (9) | −0.0040 (9) | −0.0061 (9) |
| C1 | 0.0467 (16) | 0.0283 (16) | 0.0354 (14) | 0.0026 (13) | −0.0017 (12) | 0.0011 (12) |
| C2 | 0.0396 (15) | 0.0312 (15) | 0.0376 (14) | −0.0008 (12) | 0.0009 (12) | 0.0058 (12) |
| C3 | 0.0364 (15) | 0.0312 (15) | 0.0380 (14) | −0.0059 (12) | −0.0040 (11) | 0.0003 (12) |
| C4 | 0.0413 (16) | 0.0339 (16) | 0.0351 (15) | −0.0025 (13) | −0.0059 (12) | −0.0018 (13) |
| C5 | 0.0348 (14) | 0.0275 (15) | 0.0351 (14) | 0.0032 (11) | −0.0015 (11) | 0.0025 (11) |
| C6 | 0.0389 (15) | 0.0378 (17) | 0.0362 (15) | −0.0007 (13) | −0.0059 (12) | −0.0006 (13) |
| C7 | 0.0443 (16) | 0.0386 (17) | 0.0364 (15) | 0.0044 (14) | 0.0039 (12) | −0.0004 (13) |
| C8 | 0.0340 (15) | 0.0359 (17) | 0.0521 (18) | 0.0043 (13) | 0.0035 (13) | 0.0038 (14) |
| C9 | 0.0344 (15) | 0.0430 (18) | 0.0516 (18) | −0.0021 (13) | −0.0069 (13) | −0.0070 (14) |
| C10 | 0.0423 (15) | 0.0387 (17) | 0.0330 (14) | 0.0028 (13) | −0.0018 (12) | −0.0036 (12) |
| C11 | 0.0461 (17) | 0.0462 (18) | 0.0355 (15) | −0.0017 (14) | −0.0021 (12) | 0.0004 (13) |
| C12 | 0.0538 (19) | 0.050 (2) | 0.0523 (18) | −0.0059 (16) | 0.0158 (15) | −0.0042 (16) |
| C13 | 0.0371 (16) | 0.049 (2) | 0.065 (2) | −0.0053 (14) | 0.0093 (15) | −0.0124 (16) |
| C14 | 0.0392 (15) | 0.0390 (17) | 0.0510 (17) | 0.0016 (14) | −0.0083 (13) | −0.0028 (14) |
| Cl1—C8 | 1.740 (3) | C5—C6 | 1.382 (3) |
| N1—C4 | 1.392 (3) | C6—C7 | 1.380 (3) |
| N1—C1 | 1.400 (3) | C6—H6 | 0.9300 |
| N1—C5 | 1.432 (3) | C7—C8 | 1.369 (4) |
| O1—C1 | 1.199 (3) | C7—H7 | 0.9300 |
| O2—C4 | 1.204 (3) | C8—C9 | 1.378 (4) |
| O3—C11 | 1.431 (3) | C9—C10 | 1.376 (4) |
| O3—C14 | 1.440 (3) | C9—H9 | 0.9300 |
| C1—C2 | 1.496 (4) | C10—H10 | 0.9300 |
| C2—C3 | 1.533 (3) | C11—C12 | 1.508 (4) |
| C2—C11 | 1.563 (4) | C11—H11 | 0.9800 |
| C2—H2 | 0.9800 | C12—C13 | 1.313 (4) |
| C3—C4 | 1.505 (4) | C12—H12 | 0.9300 |
| C3—C14 | 1.547 (4) | C13—C14 | 1.503 (4) |
| C3—H3 | 0.9800 | C13—H13 | 0.9300 |
| C5—C10 | 1.380 (3) | C14—H14 | 0.9800 |
| C4—N1—C1 | 112.4 (2) | C8—C7—H7 | 120.4 |
| C4—N1—C5 | 123.6 (2) | C6—C7—H7 | 120.4 |
| C1—N1—C5 | 123.9 (2) | C7—C8—C9 | 121.3 (2) |
| C11—O3—C14 | 95.76 (19) | C7—C8—Cl1 | 119.7 (2) |
| O1—C1—N1 | 124.2 (2) | C9—C8—Cl1 | 118.9 (2) |
| O1—C1—C2 | 127.6 (2) | C10—C9—C8 | 119.5 (3) |
| N1—C1—C2 | 108.2 (2) | C10—C9—H9 | 120.3 |
| C1—C2—C3 | 105.7 (2) | C8—C9—H9 | 120.3 |
| C1—C2—C11 | 112.4 (2) | C9—C10—C5 | 119.7 (2) |
| C3—C2—C11 | 100.1 (2) | C9—C10—H10 | 120.1 |
| C1—C2—H2 | 112.6 | C5—C10—H10 | 120.1 |
| C3—C2—H2 | 112.6 | O3—C11—C12 | 102.6 (2) |
| C11—C2—H2 | 112.6 | O3—C11—C2 | 101.68 (19) |
| C4—C3—C2 | 104.6 (2) | C12—C11—C2 | 104.8 (2) |
| C4—C3—C14 | 110.5 (2) | O3—C11—H11 | 115.3 |
| C2—C3—C14 | 101.9 (2) | C12—C11—H11 | 115.3 |
| C4—C3—H3 | 113.0 | C2—C11—H11 | 115.3 |
| C2—C3—H3 | 113.0 | C13—C12—C11 | 105.2 (3) |
| C14—C3—H3 | 113.0 | C13—C12—H12 | 127.4 |
| O2—C4—N1 | 124.4 (2) | C11—C12—H12 | 127.4 |
| O2—C4—C3 | 126.8 (2) | C12—C13—C14 | 106.3 (3) |
| N1—C4—C3 | 108.8 (2) | C12—C13—H13 | 126.9 |
| C10—C5—C6 | 120.3 (2) | C14—C13—H13 | 126.9 |
| C10—C5—N1 | 119.4 (2) | O3—C14—C13 | 101.9 (2) |
| C6—C5—N1 | 120.3 (2) | O3—C14—C3 | 99.7 (2) |
| C7—C6—C5 | 119.9 (2) | C13—C14—C3 | 107.0 (2) |
| C7—C6—H6 | 120.1 | O3—C14—H14 | 115.4 |
| C5—C6—H6 | 120.1 | C13—C14—H14 | 115.4 |
| C8—C7—C6 | 119.3 (2) | C3—C14—H14 | 115.4 |
| C4—N1—C1—O1 | 179.0 (3) | C5—C6—C7—C8 | 0.8 (4) |
| C5—N1—C1—O1 | −4.8 (4) | C6—C7—C8—C9 | −0.8 (4) |
| C4—N1—C1—C2 | −1.9 (3) | C6—C7—C8—Cl1 | −179.9 (2) |
| C5—N1—C1—C2 | 174.3 (2) | C7—C8—C9—C10 | 0.4 (4) |
| O1—C1—C2—C3 | −176.4 (3) | Cl1—C8—C9—C10 | 179.5 (2) |
| N1—C1—C2—C3 | 4.5 (3) | C8—C9—C10—C5 | 0.2 (4) |
| O1—C1—C2—C11 | 75.3 (4) | C6—C5—C10—C9 | −0.2 (4) |
| N1—C1—C2—C11 | −103.8 (2) | N1—C5—C10—C9 | −178.5 (2) |
| C1—C2—C3—C4 | −5.3 (3) | C14—O3—C11—C12 | −49.2 (2) |
| C11—C2—C3—C4 | 111.7 (2) | C14—O3—C11—C2 | 59.1 (2) |
| C1—C2—C3—C14 | −120.4 (2) | C1—C2—C11—O3 | 78.3 (2) |
| C11—C2—C3—C14 | −3.5 (2) | C3—C2—C11—O3 | −33.5 (2) |
| C1—N1—C4—O2 | 176.7 (3) | C1—C2—C11—C12 | −175.1 (2) |
| C5—N1—C4—O2 | 0.4 (4) | C3—C2—C11—C12 | 73.1 (2) |
| C1—N1—C4—C3 | −1.6 (3) | O3—C11—C12—C13 | 31.7 (3) |
| C5—N1—C4—C3 | −177.9 (2) | C2—C11—C12—C13 | −74.2 (3) |
| C2—C3—C4—O2 | −173.9 (3) | C11—C12—C13—C14 | 0.3 (3) |
| C14—C3—C4—O2 | −65.0 (4) | C11—O3—C14—C13 | 49.1 (2) |
| C2—C3—C4—N1 | 4.3 (3) | C11—O3—C14—C3 | −60.8 (2) |
| C14—C3—C4—N1 | 113.3 (2) | C12—C13—C14—O3 | −31.9 (3) |
| C4—N1—C5—C10 | 128.6 (3) | C12—C13—C14—C3 | 72.3 (3) |
| C1—N1—C5—C10 | −47.3 (4) | C4—C3—C14—O3 | −71.6 (2) |
| C4—N1—C5—C6 | −49.7 (4) | C2—C3—C14—O3 | 39.1 (2) |
| C1—N1—C5—C6 | 134.5 (3) | C4—C3—C14—C13 | −177.4 (2) |
| C10—C5—C6—C7 | −0.2 (4) | C2—C3—C14—C13 | −66.7 (3) |
| N1—C5—C6—C7 | 178.0 (2) |
Experimental details
| Crystal data | |
| Chemical formula | C14H10ClNO3 |
| Mr | 275.68 |
| Crystal system, space group | Monoclinic, P21/c |
| Temperature (K) | 298 |
| a, b, c (Å) | 10.4946 (11), 8.2890 (8), 14.0871 (13) |
| β (°) | 91.538 (1) |
| V (Å3) | 1225.0 (2) |
| Z | 4 |
| Radiation type | Mo Kα |
| µ (mm−1) | 0.31 |
| Crystal size (mm) | 0.40 × 0.33 × 0.21 |
| Data collection | |
| Diffractometer | Bruker SMART CCD area-detector |
| Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
| Tmin, Tmax | 0.885, 0.937 |
| No. of measured, independent and observed [I > 2σ(I)] reflections | 5907, 2156, 1466 |
| Rint | 0.040 |
| (sin θ/λ)max (Å−1) | 0.595 |
| Refinement | |
| R[F2 > 2σ(F2)], wR(F2), S | 0.043, 0.113, 1.07 |
| No. of reflections | 2156 |
| No. of parameters | 172 |
| H-atom treatment | H-atom parameters constrained |
| Δρmax, Δρmin (e Å−3) | 0.25, −0.33 |
Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
Acknowledgements
This work was supported by the Shandong Provincial Natural Science Foundation, China (ZR2009BL027)
References
Bruker (1997). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Deng, L. P. & Hu, Y. Z. (2007). J. Heterocycl. Chem. 44, 597–601. CrossRef CAS Google Scholar
Goh, Y. W., Pool, B. R. & White, J. M. (2008). J. Org. Chem. 73, 151–156. Web of Science CSD CrossRef PubMed CAS Google Scholar
Hart, M. E., Chamberlin, A. R., Walkom, C., Sakoff, J. A. & McCluskey, A. (2004). Bioorg. Med. Chem. Lett. 14, 1969–1973. Web of Science CrossRef PubMed CAS Google Scholar
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Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
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| CRYSTALLOGRAPHIC COMMUNICATIONS |
7-Oxa-bicyclo[2,2,1]hept-5-ene-2,3-dicarboxylic anhydride has been widely employed in clinical practice, as it is less toxic and much easier to be synthesized (Deng & Hu, 2007). Its derivatives are also pharmacologically active (Hart et al., 2004). In this paper, the structure of the title compound, (I), is reported (Fig. 1). The bond lengths and angles are as expected and comparable to those in the similar compounds (Goh et al., 2008). The dihedral angle between the pyrrolidine-2,5-dione plane and 4-chlorophenyl plane is 49.0 (2)°.