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Acta Crystallogr Sect E Struct Rep Online. 2010 December 1; 66(Pt 12): o3238.
Published online 2010 November 20. doi:  10.1107/S1600536810047537
PMCID: PMC3011550

N-(4-Chloro­phen­yl)-7-oxabicyclo­[2.2.1]hept-5-ene-2,3-dicarboximide

Abstract

In the title racemic compound, 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 [triangle]). For related structures, see: Goh et al. (2008 [triangle]); Hart et al. (2004 [triangle]).

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Object name is e-66-o3238-scheme1.jpg

Experimental

Crystal data

  • C14H10ClNO3
  • M r = 275.68
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-o3238-efi1.jpg
  • a = 10.4946 (11) Å
  • b = 8.2890 (8) Å
  • c = 14.0871 (13) Å
  • β = 91.538 (1)°
  • V = 1225.0 (2) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.31 mm−1
  • T = 298 K
  • 0.40 × 0.33 × 0.21 mm

Data collection

  • Bruker SMART CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996 [triangle]) T min = 0.885, T max = 0.937
  • 5907 measured reflections
  • 2156 independent reflections
  • 1466 reflections with I > 2σ(I)
  • R int = 0.040

Refinement

  • R[F 2 > 2σ(F 2)] = 0.043
  • wR(F 2) = 0.113
  • S = 1.07
  • 2156 reflections
  • 172 parameters
  • H-atom parameters constrained
  • Δρmax = 0.25 e Å−3
  • Δρmin = −0.33 e Å−3

Data collection: SMART (Bruker, 1997 [triangle]); cell refinement: SAINT (Bruker, 1997 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810047537/is2633sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810047537/is2633Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

This work was supported by the Shandong Provincial Natural Science Foundation, China (ZR2009BL027)

supplementary crystallographic information

Comment

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)°.

Experimental

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.

Refinement

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).

Figures

Fig. 1.
The molecular structure of (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at 30% probability level.

Crystal data

C14H10ClNO3F(000) = 568
Mr = 275.68Dx = 1.495 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 1615 reflections
a = 10.4946 (11) Åθ = 2.9–24.8°
b = 8.2890 (8) ŵ = 0.31 mm1
c = 14.0871 (13) ÅT = 298 K
β = 91.538 (1)°Block, light yellow
V = 1225.0 (2) Å30.40 × 0.33 × 0.21 mm
Z = 4

Data collection

Bruker SMART CCD area-detector diffractometer2156 independent reflections
Radiation source: fine-focus sealed tube1466 reflections with I > 2σ(I)
graphiteRint = 0.040
[var phi] and ω scansθmax = 25.0°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)h = −12→12
Tmin = 0.885, Tmax = 0.937k = −9→9
5907 measured reflectionsl = −13→16

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.043Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.113H-atom parameters constrained
S = 1.07w = 1/[σ2(Fo2) + (0.0446P)2 + 0.4264P] where P = (Fo2 + 2Fc2)/3
2156 reflections(Δ/σ)max < 0.001
172 parametersΔρmax = 0.25 e Å3
0 restraintsΔρmin = −0.33 e Å3

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

xyzUiso*/Ueq
Cl11.06821 (7)0.52842 (11)0.16059 (6)0.0601 (3)
N10.58629 (19)0.2856 (3)0.31440 (13)0.0349 (5)
O10.66611 (17)0.1666 (3)0.45091 (12)0.0482 (5)
O20.45183 (18)0.3870 (3)0.19755 (13)0.0556 (6)
O30.37280 (17)0.4471 (2)0.44140 (13)0.0444 (5)
C10.5766 (3)0.2056 (3)0.40149 (18)0.0369 (6)
C20.4383 (2)0.1821 (3)0.42057 (17)0.0361 (6)
H20.41760.06970.43540.043*
C30.3661 (2)0.2439 (3)0.33183 (17)0.0353 (6)
H30.31570.15980.29940.042*
C40.4678 (2)0.3141 (3)0.27085 (18)0.0369 (6)
C50.7041 (2)0.3409 (3)0.27702 (17)0.0325 (6)
C60.7316 (2)0.3134 (3)0.18301 (17)0.0377 (7)
H60.67480.25580.14420.045*
C70.8436 (2)0.3715 (3)0.14685 (18)0.0397 (7)
H70.86230.35450.08350.048*
C80.9268 (2)0.4544 (3)0.2053 (2)0.0407 (7)
C90.9002 (2)0.4827 (3)0.2991 (2)0.0432 (7)
H90.95750.53980.33770.052*
C100.7882 (2)0.4258 (3)0.33505 (18)0.0381 (7)
H100.76920.44450.39820.046*
C110.3888 (3)0.3030 (4)0.49633 (18)0.0427 (7)
H110.44270.31380.55390.051*
C120.2531 (3)0.2520 (4)0.5124 (2)0.0519 (8)
H120.22200.19810.56480.062*
C130.1885 (3)0.3001 (4)0.4365 (2)0.0501 (8)
H130.10150.28750.42430.060*
C140.2830 (2)0.3796 (3)0.37332 (19)0.0432 (7)
H140.24690.45590.32680.052*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Cl10.0375 (4)0.0665 (6)0.0769 (6)−0.0031 (4)0.0100 (4)0.0018 (4)
N10.0347 (12)0.0361 (14)0.0336 (12)−0.0010 (10)−0.0036 (9)0.0051 (10)
O10.0459 (12)0.0553 (14)0.0429 (11)0.0061 (10)−0.0086 (9)0.0132 (10)
O20.0503 (12)0.0730 (16)0.0430 (12)0.0006 (11)−0.0072 (9)0.0236 (11)
O30.0454 (11)0.0324 (11)0.0551 (12)−0.0050 (9)−0.0040 (9)−0.0061 (9)
C10.0467 (16)0.0283 (16)0.0354 (14)0.0026 (13)−0.0017 (12)0.0011 (12)
C20.0396 (15)0.0312 (15)0.0376 (14)−0.0008 (12)0.0009 (12)0.0058 (12)
C30.0364 (15)0.0312 (15)0.0380 (14)−0.0059 (12)−0.0040 (11)0.0003 (12)
C40.0413 (16)0.0339 (16)0.0351 (15)−0.0025 (13)−0.0059 (12)−0.0018 (13)
C50.0348 (14)0.0275 (15)0.0351 (14)0.0032 (11)−0.0015 (11)0.0025 (11)
C60.0389 (15)0.0378 (17)0.0362 (15)−0.0007 (13)−0.0059 (12)−0.0006 (13)
C70.0443 (16)0.0386 (17)0.0364 (15)0.0044 (14)0.0039 (12)−0.0004 (13)
C80.0340 (15)0.0359 (17)0.0521 (18)0.0043 (13)0.0035 (13)0.0038 (14)
C90.0344 (15)0.0430 (18)0.0516 (18)−0.0021 (13)−0.0069 (13)−0.0070 (14)
C100.0423 (15)0.0387 (17)0.0330 (14)0.0028 (13)−0.0018 (12)−0.0036 (12)
C110.0461 (17)0.0462 (18)0.0355 (15)−0.0017 (14)−0.0021 (12)0.0004 (13)
C120.0538 (19)0.050 (2)0.0523 (18)−0.0059 (16)0.0158 (15)−0.0042 (16)
C130.0371 (16)0.049 (2)0.065 (2)−0.0053 (14)0.0093 (15)−0.0124 (16)
C140.0392 (15)0.0390 (17)0.0510 (17)0.0016 (14)−0.0083 (13)−0.0028 (14)

Geometric parameters (Å, °)

Cl1—C81.740 (3)C5—C61.382 (3)
N1—C41.392 (3)C6—C71.380 (3)
N1—C11.400 (3)C6—H60.9300
N1—C51.432 (3)C7—C81.369 (4)
O1—C11.199 (3)C7—H70.9300
O2—C41.204 (3)C8—C91.378 (4)
O3—C111.431 (3)C9—C101.376 (4)
O3—C141.440 (3)C9—H90.9300
C1—C21.496 (4)C10—H100.9300
C2—C31.533 (3)C11—C121.508 (4)
C2—C111.563 (4)C11—H110.9800
C2—H20.9800C12—C131.313 (4)
C3—C41.505 (4)C12—H120.9300
C3—C141.547 (4)C13—C141.503 (4)
C3—H30.9800C13—H130.9300
C5—C101.380 (3)C14—H140.9800
C4—N1—C1112.4 (2)C8—C7—H7120.4
C4—N1—C5123.6 (2)C6—C7—H7120.4
C1—N1—C5123.9 (2)C7—C8—C9121.3 (2)
C11—O3—C1495.76 (19)C7—C8—Cl1119.7 (2)
O1—C1—N1124.2 (2)C9—C8—Cl1118.9 (2)
O1—C1—C2127.6 (2)C10—C9—C8119.5 (3)
N1—C1—C2108.2 (2)C10—C9—H9120.3
C1—C2—C3105.7 (2)C8—C9—H9120.3
C1—C2—C11112.4 (2)C9—C10—C5119.7 (2)
C3—C2—C11100.1 (2)C9—C10—H10120.1
C1—C2—H2112.6C5—C10—H10120.1
C3—C2—H2112.6O3—C11—C12102.6 (2)
C11—C2—H2112.6O3—C11—C2101.68 (19)
C4—C3—C2104.6 (2)C12—C11—C2104.8 (2)
C4—C3—C14110.5 (2)O3—C11—H11115.3
C2—C3—C14101.9 (2)C12—C11—H11115.3
C4—C3—H3113.0C2—C11—H11115.3
C2—C3—H3113.0C13—C12—C11105.2 (3)
C14—C3—H3113.0C13—C12—H12127.4
O2—C4—N1124.4 (2)C11—C12—H12127.4
O2—C4—C3126.8 (2)C12—C13—C14106.3 (3)
N1—C4—C3108.8 (2)C12—C13—H13126.9
C10—C5—C6120.3 (2)C14—C13—H13126.9
C10—C5—N1119.4 (2)O3—C14—C13101.9 (2)
C6—C5—N1120.3 (2)O3—C14—C399.7 (2)
C7—C6—C5119.9 (2)C13—C14—C3107.0 (2)
C7—C6—H6120.1O3—C14—H14115.4
C5—C6—H6120.1C13—C14—H14115.4
C8—C7—C6119.3 (2)C3—C14—H14115.4
C4—N1—C1—O1179.0 (3)C5—C6—C7—C80.8 (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—C2174.3 (2)C7—C8—C9—C100.4 (4)
O1—C1—C2—C3−176.4 (3)Cl1—C8—C9—C10179.5 (2)
N1—C1—C2—C34.5 (3)C8—C9—C10—C50.2 (4)
O1—C1—C2—C1175.3 (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—C4111.7 (2)C14—O3—C11—C259.1 (2)
C1—C2—C3—C14−120.4 (2)C1—C2—C11—O378.3 (2)
C11—C2—C3—C14−3.5 (2)C3—C2—C11—O3−33.5 (2)
C1—N1—C4—O2176.7 (3)C1—C2—C11—C12−175.1 (2)
C5—N1—C4—O20.4 (4)C3—C2—C11—C1273.1 (2)
C1—N1—C4—C3−1.6 (3)O3—C11—C12—C1331.7 (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—C140.3 (3)
C14—C3—C4—O2−65.0 (4)C11—O3—C14—C1349.1 (2)
C2—C3—C4—N14.3 (3)C11—O3—C14—C3−60.8 (2)
C14—C3—C4—N1113.3 (2)C12—C13—C14—O3−31.9 (3)
C4—N1—C5—C10128.6 (3)C12—C13—C14—C372.3 (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—O339.1 (2)
C1—N1—C5—C6134.5 (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—C7178.0 (2)

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: IS2633).

References

  • Bruker (1997). SMART and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  • Deng, L. P. & Hu, Y. Z. (2007). J. Heterocycl. Chem.44, 597–601.
  • Goh, Y. W., Pool, B. R. & White, J. M. (2008). J. Org. Chem.73, 151–156. [PubMed]
  • Hart, M. E., Chamberlin, A. R., Walkom, C., Sakoff, J. A. & McCluskey, A. (2004). Bioorg. Med. Chem. Lett.14, 1969–1973. [PubMed]
  • Sheldrick, G. M. (1996). SADABS University of Göttingen, Germany.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

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