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Supporting information
 | Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801003270/ci6010sup1.cif |
 | Structure factor file (CIF format) https://doi.org/10.1107/S1600536801003270/ci6010Isup2.hkl |
CCDC reference: 159868
Key indicators
- Single-crystal X-ray study
- T = 200 K
- Mean
![[sigma]](https://journals.iucr.org/logos/entities/sigma_rmgif.gif)
(C-C) = 0.002 Å - R factor = 0.043
- wR factor = 0.112
- Data-to-parameter ratio = 16.6
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry
N-Methyl-α-bicyclo[2.2.1]hepta-2,5-dien-2-ylmethoxycarbonyl nitrone, which was generated in situ by the addition of N-methyl hydroxylamine, pyridine and 4 Å molecular sieves to oxoacetic acid bicyclo[2.2.1]hepta-2,5-dien-2-ylmethyl ester in toluene, undergoes spontaneous intramolecular cycloaddition at 358 K to provide cycloadduct (I) as the only regio- and stereoisomer. Suitable crystals were grown from an ethyl acetate/hexanes (2:8) mixture.
H atoms were allowed for as riding atoms with C—H distances in the range 0.95–1.00 Å.
Data collection: COLLECT (Nonius BV, 1997); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976) and PLATON (Spek 2001); software used to prepare material for publication: SHELXL97 and PRPKAPPA (Ferguson, 1999).
![[Figure 1]](https://journals.iucr.org/e/issues/2001/03/00/ci6010/ci6010fig1thm.gif)
| Fig. 1. A view of (I) with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. |
| C11H13NO3 | Dx = 1.394 Mg m−3 |
| Mr = 207.22 | Mo Kα radiation, λ = 0.71073 Å |
| Orthorhombic, Pbca | Cell parameters from 10386 reflections |
| a = 8.6209 (2) Å | θ = 2.6–27.5° |
| b = 13.9266 (4) Å | µ = 0.10 mm−1 |
| c = 16.4518 (6) Å | T = 200 K |
| V = 1975.2 (1) Å3 | Block, colourless |
| Z = 8 | 0.27 × 0.25 × 0.22 mm |
| F(000) = 880 |
| Nonius KappaCCD diffractometer | 2254 independent reflections |
| Radiation source: fine-focus sealed tube | 1745 reflections with I > 2σ(I) |
| Graphite monochromator | Rint = 0.022 |
| Detector resolution: 9 pixels mm-1 | θmax = 27.5°, θmin = 2.9° |
| ϕ scans, and ω scans with κ offsets | h = 0→11 |
| Absorption correction: multi-scan (DENZO-SMN; Otwinowski & Minor, 1997) | k = 0→18 |
| Tmin = 0.973, Tmax = 0.978 | l = 0→21 |
| 10386 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)] = 0.043 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.112 | H-atom parameters constrained |
| S = 1.04 | w = 1/[σ2(Fo2) + (0.0478P)2 + 0.5639P] where P = (Fo2 + 2Fc2)/3 |
| 2254 reflections | (Δ/σ)max < 0.001 |
| 136 parameters | Δρmax = 0.20 e Å−3 |
| 0 restraints | Δρmin = −0.17 e Å−3 |
| C11H13NO3 | V = 1975.2 (1) Å3 |
| Mr = 207.22 | Z = 8 |
| Orthorhombic, Pbca | Mo Kα radiation |
| a = 8.6209 (2) Å | µ = 0.10 mm−1 |
| b = 13.9266 (4) Å | T = 200 K |
| c = 16.4518 (6) Å | 0.27 × 0.25 × 0.22 mm |
| Nonius KappaCCD diffractometer | 2254 independent reflections |
| Absorption correction: multi-scan (DENZO-SMN; Otwinowski & Minor, 1997) | 1745 reflections with I > 2σ(I) |
| Tmin = 0.973, Tmax = 0.978 | Rint = 0.022 |
| 10386 measured reflections |
| R[F2 > 2σ(F2)] = 0.043 | 0 restraints |
| wR(F2) = 0.112 | H-atom parameters constrained |
| S = 1.04 | Δρmax = 0.20 e Å−3 |
| 2254 reflections | Δρmin = −0.17 e Å−3 |
| 136 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 | ||
| O1 | 0.42641 (12) | 0.21560 (7) | 0.25844 (6) | 0.0379 (3) | |
| C2 | 0.42998 (17) | 0.21490 (10) | 0.34680 (9) | 0.0343 (3) | |
| H2A | 0.4036 | 0.2792 | 0.3683 | 0.041* | |
| H2B | 0.5348 | 0.1973 | 0.3664 | 0.041* | |
| C3 | 0.31026 (15) | 0.14051 (9) | 0.37541 (8) | 0.0264 (3) | |
| C4 | 0.36981 (17) | 0.06066 (10) | 0.43369 (9) | 0.0326 (3) | |
| H4 | 0.4805 | 0.0707 | 0.4499 | 0.039* | |
| O5 | 0.34766 (13) | −0.02759 (7) | 0.39064 (6) | 0.0410 (3) | |
| N6 | 0.37311 (15) | −0.00087 (8) | 0.30506 (7) | 0.0346 (3) | |
| C7 | 0.27296 (16) | 0.08517 (9) | 0.29829 (8) | 0.0279 (3) | |
| H7 | 0.1603 | 0.0694 | 0.2925 | 0.033* | |
| C8 | 0.33540 (16) | 0.14473 (10) | 0.22928 (9) | 0.0315 (3) | |
| O9 | 0.31496 (14) | 0.13356 (8) | 0.15766 (6) | 0.0444 (3) | |
| C10 | 0.3161 (2) | −0.08135 (11) | 0.25727 (11) | 0.0501 (5) | |
| H10A | 0.3860 | −0.1363 | 0.2640 | 0.075* | |
| H10B | 0.3120 | −0.0630 | 0.1998 | 0.075* | |
| H10C | 0.2119 | −0.0989 | 0.2759 | 0.075* | |
| C11 | 0.17081 (16) | 0.18313 (10) | 0.42348 (9) | 0.0311 (3) | |
| H11 | 0.0957 | 0.2226 | 0.3914 | 0.037* | |
| C12 | 0.24296 (18) | 0.23170 (11) | 0.49703 (9) | 0.0390 (4) | |
| H12 | 0.2493 | 0.2989 | 0.5063 | 0.047* | |
| C13 | 0.29541 (19) | 0.16331 (12) | 0.54587 (10) | 0.0422 (4) | |
| H13 | 0.3469 | 0.1727 | 0.5963 | 0.051* | |
| C14 | 0.25840 (18) | 0.06717 (11) | 0.50672 (9) | 0.0375 (4) | |
| H14 | 0.2559 | 0.0103 | 0.5438 | 0.045* | |
| C15 | 0.10526 (17) | 0.09220 (10) | 0.46336 (9) | 0.0352 (3) | |
| H15A | 0.0733 | 0.0430 | 0.4233 | 0.042* | |
| H15B | 0.0194 | 0.1058 | 0.5016 | 0.042* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| O1 | 0.0441 (6) | 0.0356 (5) | 0.0339 (6) | −0.0082 (5) | 0.0081 (4) | 0.0037 (4) |
| C2 | 0.0331 (7) | 0.0365 (7) | 0.0334 (8) | −0.0068 (6) | 0.0029 (6) | 0.0008 (6) |
| C3 | 0.0233 (6) | 0.0271 (7) | 0.0287 (7) | 0.0010 (5) | −0.0004 (5) | 0.0030 (5) |
| C4 | 0.0328 (7) | 0.0332 (7) | 0.0318 (8) | 0.0050 (6) | −0.0014 (6) | 0.0049 (6) |
| O5 | 0.0554 (7) | 0.0298 (5) | 0.0378 (6) | 0.0087 (5) | 0.0039 (5) | 0.0079 (4) |
| N6 | 0.0418 (7) | 0.0280 (6) | 0.0339 (7) | 0.0062 (5) | 0.0028 (5) | 0.0020 (5) |
| C7 | 0.0258 (7) | 0.0281 (6) | 0.0298 (7) | 0.0013 (5) | 0.0001 (5) | 0.0022 (5) |
| C8 | 0.0306 (7) | 0.0328 (7) | 0.0311 (8) | 0.0046 (6) | 0.0023 (6) | 0.0036 (6) |
| O9 | 0.0509 (7) | 0.0535 (7) | 0.0289 (6) | 0.0025 (5) | 0.0021 (5) | 0.0041 (5) |
| C10 | 0.0671 (12) | 0.0321 (8) | 0.0513 (11) | 0.0009 (8) | 0.0029 (9) | −0.0066 (7) |
| C11 | 0.0273 (7) | 0.0301 (7) | 0.0358 (8) | 0.0028 (5) | 0.0037 (6) | 0.0015 (6) |
| C12 | 0.0403 (8) | 0.0389 (8) | 0.0378 (8) | −0.0051 (7) | 0.0104 (6) | −0.0073 (7) |
| C13 | 0.0408 (8) | 0.0557 (10) | 0.0301 (8) | −0.0050 (7) | 0.0031 (6) | −0.0040 (7) |
| C14 | 0.0402 (8) | 0.0416 (8) | 0.0307 (8) | 0.0000 (7) | 0.0034 (6) | 0.0086 (6) |
| C15 | 0.0311 (7) | 0.0381 (8) | 0.0365 (8) | −0.0029 (6) | 0.0064 (6) | 0.0038 (6) |
| O1—C8 | 1.3490 (18) | C8—O9 | 1.2016 (17) |
| O1—C2 | 1.4541 (18) | C10—H10A | 0.98 |
| C2—C3 | 1.5363 (18) | C10—H10B | 0.98 |
| C2—H2A | 0.99 | C10—H10C | 0.98 |
| C2—H2B | 0.99 | C11—C12 | 1.519 (2) |
| C3—C7 | 1.5190 (19) | C11—C15 | 1.5341 (19) |
| C3—C4 | 1.5555 (18) | C11—H11 | 1.00 |
| C3—C11 | 1.5566 (18) | C12—C13 | 1.326 (2) |
| C4—O5 | 1.4314 (17) | C12—H12 | 0.95 |
| C4—C14 | 1.541 (2) | C13—C14 | 1.520 (2) |
| C4—H4 | 1.00 | C13—H13 | 0.95 |
| O5—N6 | 1.4726 (15) | C14—C15 | 1.540 (2) |
| N6—C10 | 1.454 (2) | C14—H14 | 1.00 |
| N6—C7 | 1.4811 (17) | C15—H15A | 0.99 |
| C7—C8 | 1.5055 (18) | C15—H15B | 0.99 |
| C7—H7 | 1.00 | ||
| C8—O1—C2 | 111.27 (10) | O1—C8—C7 | 110.06 (12) |
| O1—C2—C3 | 107.26 (11) | N6—C10—H10A | 109.5 |
| O1—C2—H2A | 110.3 | N6—C10—H10B | 109.5 |
| C3—C2—H2A | 110.3 | H10A—C10—H10B | 109.5 |
| O1—C2—H2B | 110.3 | N6—C10—H10C | 109.5 |
| C3—C2—H2B | 110.3 | H10A—C10—H10C | 109.5 |
| H2A—C2—H2B | 108.5 | H10B—C10—H10C | 109.5 |
| C7—C3—C2 | 103.21 (11) | C12—C11—C15 | 100.24 (12) |
| C7—C3—C4 | 102.83 (10) | C12—C11—C3 | 104.96 (11) |
| C2—C3—C4 | 116.70 (11) | C15—C11—C3 | 100.78 (10) |
| C7—C3—C11 | 117.02 (11) | C12—C11—H11 | 116.2 |
| C2—C3—C11 | 114.67 (11) | C15—C11—H11 | 116.2 |
| C4—C3—C11 | 102.38 (11) | C3—C11—H11 | 116.2 |
| O5—C4—C14 | 110.68 (12) | C13—C12—C11 | 107.60 (13) |
| O5—C4—C3 | 105.35 (11) | C13—C12—H12 | 126.2 |
| C14—C4—C3 | 103.47 (11) | C11—C12—H12 | 126.2 |
| O5—C4—H4 | 112.3 | C12—C13—C14 | 107.73 (14) |
| C14—C4—H4 | 112.3 | C12—C13—H13 | 126.1 |
| C3—C4—H4 | 112.3 | C14—C13—H13 | 126.1 |
| C4—O5—N6 | 103.66 (9) | C13—C14—C15 | 100.19 (12) |
| C10—N6—O5 | 105.77 (11) | C13—C14—C4 | 104.56 (12) |
| C10—N6—C7 | 112.69 (12) | C15—C14—C4 | 100.74 (11) |
| O5—N6—C7 | 100.93 (10) | C13—C14—H14 | 116.3 |
| N6—C7—C8 | 107.11 (11) | C15—C14—H14 | 116.3 |
| N6—C7—C3 | 102.95 (10) | C4—C14—H14 | 116.3 |
| C8—C7—C3 | 105.94 (11) | C11—C15—C14 | 93.97 (11) |
| N6—C7—H7 | 113.3 | C11—C15—H15A | 112.9 |
| C8—C7—H7 | 113.3 | C14—C15—H15A | 112.9 |
| C3—C7—H7 | 113.3 | C11—C15—H15B | 112.9 |
| O9—C8—O1 | 121.91 (13) | C14—C15—H15B | 112.9 |
| O9—C8—C7 | 128.01 (14) | H15A—C15—H15B | 110.3 |
Experimental details
| Crystal data | |
| Chemical formula | C11H13NO3 |
| Mr | 207.22 |
| Crystal system, space group | Orthorhombic, Pbca |
| Temperature (K) | 200 |
| a, b, c (Å) | 8.6209 (2), 13.9266 (4), 16.4518 (6) |
| V (Å3) | 1975.2 (1) |
| Z | 8 |
| Radiation type | Mo Kα |
| µ (mm−1) | 0.10 |
| Crystal size (mm) | 0.27 × 0.25 × 0.22 |
| Data collection | |
| Diffractometer | Nonius KappaCCD diffractometer |
| Absorption correction | Multi-scan (DENZO-SMN; Otwinowski & Minor, 1997) |
| Tmin, Tmax | 0.973, 0.978 |
| No. of measured, independent and observed [I > 2σ(I)] reflections | 10386, 2254, 1745 |
| Rint | 0.022 |
| (sin θ/λ)max (Å−1) | 0.649 |
| Refinement | |
| R[F2 > 2σ(F2)], wR(F2), S | 0.043, 0.112, 1.04 |
| No. of reflections | 2254 |
| No. of parameters | 136 |
| H-atom treatment | H-atom parameters constrained |
| Δρmax, Δρmin (e Å−3) | 0.20, −0.17 |
Computer programs: COLLECT (Nonius BV, 1997), DENZO-SMN (Otwinowski & Minor, 1997), DENZO-SMN, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEPII (Johnson, 1976) and PLATON (Spek 2001), SHELXL97 and PRPKAPPA (Ferguson, 1999).
| O1—C8 | 1.3490 (18) | N6—C10 | 1.454 (2) |
| O1—C2 | 1.4541 (18) | N6—C7 | 1.4811 (17) |
| C2—C3 | 1.5363 (18) | C7—C8 | 1.5055 (18) |
| C3—C7 | 1.5190 (19) | C8—O9 | 1.2016 (17) |
| C3—C4 | 1.5555 (18) | C11—C12 | 1.519 (2) |
| C3—C11 | 1.5566 (18) | C11—C15 | 1.5341 (19) |
| C4—O5 | 1.4314 (17) | C12—C13 | 1.326 (2) |
| C4—C14 | 1.541 (2) | C13—C14 | 1.520 (2) |
| O5—N6 | 1.4726 (15) | C14—C15 | 1.540 (2) |
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Recently, we reported the first examples of intramolecular 1,3-dipolar cycloadditions of norbornadiene-tethered nitrones (Tranmer et al., 2000). Although eight different regio- and stereoisomers could be formed in the cycloaddition of N-methyl-α-bicyclo[2.2.1]hepta-2,5-dien-2-ylmethoxycarbonyl nitrone, a single cycloadduct, (I), was obtained. The regio- and stereochemistry of the cycloadduct was established by our single-crystal X-ray diffraction analysis as shown in the scheme and Fig. 1.