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The regio- and stereochemistry of the title compound, C11H13NO3, has been established. The geometric parameters show normal values.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801003270/ci6010sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536801003270/ci6010Isup2.hkl
Contains datablock I

CCDC reference: 159868

Key indicators

  • Single-crystal X-ray study
  • T = 200 K
  • Mean [sigma](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




Comment top

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.

Experimental top

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.

Refinement top

H atoms were allowed for as riding atoms with C—H distances in the range 0.95–1.00 Å.

Computing details top

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).

Figures top
[Figure 1] Fig. 1. A view of (I) with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
6,9-Methano-4-methyl-3a,4,5a,6,9,10-hexahydro-5-oxa-1H,3H-furano[3,4-c]- isoindol-3-one top
Crystal data top
C11H13NO3Dx = 1.394 Mg m3
Mr = 207.22Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, PbcaCell parameters from 10386 reflections
a = 8.6209 (2) Åθ = 2.6–27.5°
b = 13.9266 (4) ŵ = 0.10 mm1
c = 16.4518 (6) ÅT = 200 K
V = 1975.2 (1) Å3Block, colourless
Z = 80.27 × 0.25 × 0.22 mm
F(000) = 880
Data collection top
Nonius KappaCCD
diffractometer
2254 independent reflections
Radiation source: fine-focus sealed tube1745 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.022
Detector resolution: 9 pixels mm-1θmax = 27.5°, θmin = 2.9°
ϕ scans, and ω scans with κ offsetsh = 011
Absorption correction: multi-scan
(DENZO-SMN; Otwinowski & Minor, 1997)
k = 018
Tmin = 0.973, Tmax = 0.978l = 021
10386 measured reflections
Refinement top
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) = 0.112H-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 parametersΔρmax = 0.20 e Å3
0 restraintsΔρmin = 0.17 e Å3
Crystal data top
C11H13NO3V = 1975.2 (1) Å3
Mr = 207.22Z = 8
Orthorhombic, PbcaMo Kα radiation
a = 8.6209 (2) ŵ = 0.10 mm1
b = 13.9266 (4) ÅT = 200 K
c = 16.4518 (6) Å0.27 × 0.25 × 0.22 mm
Data collection top
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 = 0.978Rint = 0.022
10386 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0430 restraints
wR(F2) = 0.112H-atom parameters constrained
S = 1.04Δρmax = 0.20 e Å3
2254 reflectionsΔρmin = 0.17 e Å3
136 parameters
Special details top

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) top
xyzUiso*/Ueq
O10.42641 (12)0.21560 (7)0.25844 (6)0.0379 (3)
C20.42998 (17)0.21490 (10)0.34680 (9)0.0343 (3)
H2A0.40360.27920.36830.041*
H2B0.53480.19730.36640.041*
C30.31026 (15)0.14051 (9)0.37541 (8)0.0264 (3)
C40.36981 (17)0.06066 (10)0.43369 (9)0.0326 (3)
H40.48050.07070.44990.039*
O50.34766 (13)0.02759 (7)0.39064 (6)0.0410 (3)
N60.37311 (15)0.00087 (8)0.30506 (7)0.0346 (3)
C70.27296 (16)0.08517 (9)0.29829 (8)0.0279 (3)
H70.16030.06940.29250.033*
C80.33540 (16)0.14473 (10)0.22928 (9)0.0315 (3)
O90.31496 (14)0.13356 (8)0.15766 (6)0.0444 (3)
C100.3161 (2)0.08135 (11)0.25727 (11)0.0501 (5)
H10A0.38600.13630.26400.075*
H10B0.31200.06300.19980.075*
H10C0.21190.09890.27590.075*
C110.17081 (16)0.18313 (10)0.42348 (9)0.0311 (3)
H110.09570.22260.39140.037*
C120.24296 (18)0.23170 (11)0.49703 (9)0.0390 (4)
H120.24930.29890.50630.047*
C130.29541 (19)0.16331 (12)0.54587 (10)0.0422 (4)
H130.34690.17270.59630.051*
C140.25840 (18)0.06717 (11)0.50672 (9)0.0375 (4)
H140.25590.01030.54380.045*
C150.10526 (17)0.09220 (10)0.46336 (9)0.0352 (3)
H15A0.07330.04300.42330.042*
H15B0.01940.10580.50160.042*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0441 (6)0.0356 (5)0.0339 (6)0.0082 (5)0.0081 (4)0.0037 (4)
C20.0331 (7)0.0365 (7)0.0334 (8)0.0068 (6)0.0029 (6)0.0008 (6)
C30.0233 (6)0.0271 (7)0.0287 (7)0.0010 (5)0.0004 (5)0.0030 (5)
C40.0328 (7)0.0332 (7)0.0318 (8)0.0050 (6)0.0014 (6)0.0049 (6)
O50.0554 (7)0.0298 (5)0.0378 (6)0.0087 (5)0.0039 (5)0.0079 (4)
N60.0418 (7)0.0280 (6)0.0339 (7)0.0062 (5)0.0028 (5)0.0020 (5)
C70.0258 (7)0.0281 (6)0.0298 (7)0.0013 (5)0.0001 (5)0.0022 (5)
C80.0306 (7)0.0328 (7)0.0311 (8)0.0046 (6)0.0023 (6)0.0036 (6)
O90.0509 (7)0.0535 (7)0.0289 (6)0.0025 (5)0.0021 (5)0.0041 (5)
C100.0671 (12)0.0321 (8)0.0513 (11)0.0009 (8)0.0029 (9)0.0066 (7)
C110.0273 (7)0.0301 (7)0.0358 (8)0.0028 (5)0.0037 (6)0.0015 (6)
C120.0403 (8)0.0389 (8)0.0378 (8)0.0051 (7)0.0104 (6)0.0073 (7)
C130.0408 (8)0.0557 (10)0.0301 (8)0.0050 (7)0.0031 (6)0.0040 (7)
C140.0402 (8)0.0416 (8)0.0307 (8)0.0000 (7)0.0034 (6)0.0086 (6)
C150.0311 (7)0.0381 (8)0.0365 (8)0.0029 (6)0.0064 (6)0.0038 (6)
Geometric parameters (Å, º) top
O1—C81.3490 (18)C8—O91.2016 (17)
O1—C21.4541 (18)C10—H10A0.98
C2—C31.5363 (18)C10—H10B0.98
C2—H2A0.99C10—H10C0.98
C2—H2B0.99C11—C121.519 (2)
C3—C71.5190 (19)C11—C151.5341 (19)
C3—C41.5555 (18)C11—H111.00
C3—C111.5566 (18)C12—C131.326 (2)
C4—O51.4314 (17)C12—H120.95
C4—C141.541 (2)C13—C141.520 (2)
C4—H41.00C13—H130.95
O5—N61.4726 (15)C14—C151.540 (2)
N6—C101.454 (2)C14—H141.00
N6—C71.4811 (17)C15—H15A0.99
C7—C81.5055 (18)C15—H15B0.99
C7—H71.00
C8—O1—C2111.27 (10)O1—C8—C7110.06 (12)
O1—C2—C3107.26 (11)N6—C10—H10A109.5
O1—C2—H2A110.3N6—C10—H10B109.5
C3—C2—H2A110.3H10A—C10—H10B109.5
O1—C2—H2B110.3N6—C10—H10C109.5
C3—C2—H2B110.3H10A—C10—H10C109.5
H2A—C2—H2B108.5H10B—C10—H10C109.5
C7—C3—C2103.21 (11)C12—C11—C15100.24 (12)
C7—C3—C4102.83 (10)C12—C11—C3104.96 (11)
C2—C3—C4116.70 (11)C15—C11—C3100.78 (10)
C7—C3—C11117.02 (11)C12—C11—H11116.2
C2—C3—C11114.67 (11)C15—C11—H11116.2
C4—C3—C11102.38 (11)C3—C11—H11116.2
O5—C4—C14110.68 (12)C13—C12—C11107.60 (13)
O5—C4—C3105.35 (11)C13—C12—H12126.2
C14—C4—C3103.47 (11)C11—C12—H12126.2
O5—C4—H4112.3C12—C13—C14107.73 (14)
C14—C4—H4112.3C12—C13—H13126.1
C3—C4—H4112.3C14—C13—H13126.1
C4—O5—N6103.66 (9)C13—C14—C15100.19 (12)
C10—N6—O5105.77 (11)C13—C14—C4104.56 (12)
C10—N6—C7112.69 (12)C15—C14—C4100.74 (11)
O5—N6—C7100.93 (10)C13—C14—H14116.3
N6—C7—C8107.11 (11)C15—C14—H14116.3
N6—C7—C3102.95 (10)C4—C14—H14116.3
C8—C7—C3105.94 (11)C11—C15—C1493.97 (11)
N6—C7—H7113.3C11—C15—H15A112.9
C8—C7—H7113.3C14—C15—H15A112.9
C3—C7—H7113.3C11—C15—H15B112.9
O9—C8—O1121.91 (13)C14—C15—H15B112.9
O9—C8—C7128.01 (14)H15A—C15—H15B110.3

Experimental details

Crystal data
Chemical formulaC11H13NO3
Mr207.22
Crystal system, space groupOrthorhombic, Pbca
Temperature (K)200
a, b, c (Å)8.6209 (2), 13.9266 (4), 16.4518 (6)
V3)1975.2 (1)
Z8
Radiation typeMo Kα
µ (mm1)0.10
Crystal size (mm)0.27 × 0.25 × 0.22
Data collection
DiffractometerNonius KappaCCD
diffractometer
Absorption correctionMulti-scan
(DENZO-SMN; Otwinowski & Minor, 1997)
Tmin, Tmax0.973, 0.978
No. of measured, independent and
observed [I > 2σ(I)] reflections
10386, 2254, 1745
Rint0.022
(sin θ/λ)max1)0.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.043, 0.112, 1.04
No. of reflections2254
No. of parameters136
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)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).

Selected bond lengths (Å) top
O1—C81.3490 (18)N6—C101.454 (2)
O1—C21.4541 (18)N6—C71.4811 (17)
C2—C31.5363 (18)C7—C81.5055 (18)
C3—C71.5190 (19)C8—O91.2016 (17)
C3—C41.5555 (18)C11—C121.519 (2)
C3—C111.5566 (18)C11—C151.5341 (19)
C4—O51.4314 (17)C12—C131.326 (2)
C4—C141.541 (2)C13—C141.520 (2)
O5—N61.4726 (15)C14—C151.540 (2)
 

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