Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100001086/qa0212sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270100001086/qa0212Isup2.hkl |
CCDC reference: 142947
4-(2'-Norbornadienyl)butyl nitrile oxide which was generated in situ by the addition of di-tert-butylcarbonate and 4-(dimethylamino)pyridine to 1-nitro-4-(2'-norbornadienyl)butane in toluene, undergoes spontaneous intramolecular cycloaddition at 363 K to provide cycloadduct (I) as the only regio- and stereoisomer. Suitable crystals were grown from ethyl acetate/hexanes (2:8) mixture.
Molecule (I) crystallized in the monoclinic system; space group P21/n from the systematic absences. H atoms were treated as riding atoms (C—H 0.93–0.98 Å).
Data collection: CAD-4-PC Software (Enraf-Nonius, 1992); cell refinement: SET4 and CELDIM (Enraf-Nonius, 1992); data reduction: DATRD2 in NRCVAX96 (Gabe et al., 1989); program(s) used to solve structure: SOLVER in NRCVAX96; program(s) used to refine structure: NRCVAX96 and SHELXL97 (Sheldrick, 1997); software used to prepare material for publication: NRCVAX96, SHELXL97 and WORDPERFECT macro PREP8 (Ferguson, 1998).
C12H15NO | ? #Insert any comments here. |
Mr = 189.25 | Dx = 1.267 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.7107 Å |
a = 7.640 (2) Å | Cell parameters from 25 reflections |
b = 12.7121 (14) Å | θ = 9.5–12.1° |
c = 10.2205 (7) Å | µ = 0.08 mm−1 |
β = 91.668 (11)° | T = 294 K |
V = 992.2 (3) Å3 | Plate, colorless |
Z = 4 | 0.42 × 0.42 × 0.19 mm |
F(000) = 408 |
Enraf-Nonius CAD-4 diffractometer | Rint = 0.011 |
Radiation source: X-ray tube | θmax = 25.5°, θmin = 2.6° |
Graphite monochromator | h = −9→9 |
θ/2θ scans | k = 0→15 |
1997 measured reflections | l = 0→12 |
1860 independent reflections | 3 standard reflections every 120 min |
1314 reflections with I > 2σ(I) | intensity decay: 6.2% |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.044 | H-atom parameters constrained |
wR(F2) = 0.109 | w = 1/[σ2(Fo2) + (0.0523P)2 + 0.076P] where P = (Fo2 + 2Fc2)/3 |
S = 1.04 | (Δ/σ)max < 0.001 |
1860 reflections | Δρmax = 0.17 e Å−3 |
129 parameters | Δρmin = −0.14 e Å−3 |
0 restraints | Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.103 (7) |
C12H15NO | V = 992.2 (3) Å3 |
Mr = 189.25 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 7.640 (2) Å | µ = 0.08 mm−1 |
b = 12.7121 (14) Å | T = 294 K |
c = 10.2205 (7) Å | 0.42 × 0.42 × 0.19 mm |
β = 91.668 (11)° |
Enraf-Nonius CAD-4 diffractometer | Rint = 0.011 |
1997 measured reflections | 3 standard reflections every 120 min |
1860 independent reflections | intensity decay: 6.2% |
1314 reflections with I > 2σ(I) |
R[F2 > 2σ(F2)] = 0.044 | 0 restraints |
wR(F2) = 0.109 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.17 e Å−3 |
1860 reflections | Δρmin = −0.14 e Å−3 |
129 parameters |
x | y | z | Uiso*/Ueq | ||
O1 | 0.21653 (16) | 0.27567 (10) | 0.05223 (11) | 0.0467 (4) | |
N1 | 0.0809 (2) | 0.35228 (11) | 0.03739 (14) | 0.0453 (4) | |
C1 | 0.1863 (3) | 0.11372 (14) | 0.18024 (18) | 0.0474 (5) | |
C2 | 0.2196 (2) | 0.23317 (13) | 0.18701 (16) | 0.0373 (4) | |
C3 | 0.0493 (2) | 0.27558 (12) | 0.24506 (15) | 0.0330 (4) | |
C4 | −0.0637 (2) | 0.17320 (13) | 0.25784 (17) | 0.0428 (5) | |
C5 | 0.0261 (3) | 0.11096 (13) | 0.36577 (19) | 0.0482 (5) | |
C6 | 0.1746 (3) | 0.07582 (14) | 0.31991 (18) | 0.0527 (5) | |
C7 | −0.0072 (3) | 0.11142 (14) | 0.13816 (19) | 0.0532 (5) | |
C8 | 0.0429 (3) | 0.34903 (14) | 0.36314 (17) | 0.0447 (5) | |
C9 | −0.1187 (3) | 0.41804 (16) | 0.3352 (2) | 0.0585 (6) | |
C10 | −0.1428 (3) | 0.42595 (15) | 0.18525 (19) | 0.0545 (5) | |
C11 | −0.0108 (2) | 0.34888 (13) | 0.13890 (16) | 0.0374 (4) | |
C12 | 0.3923 (2) | 0.26523 (17) | 0.2496 (2) | 0.0563 (5) | |
H1 | 0.2651 | 0.0737 | 0.1249 | 0.057* | |
H4 | −0.1901 | 0.1837 | 0.2658 | 0.051* | |
H5 | −0.0155 | 0.0995 | 0.4492 | 0.058* | |
H6 | 0.2572 | 0.0351 | 0.3653 | 0.063* | |
H7A | −0.0314 | 0.1481 | 0.0564 | 0.064* | |
H7B | −0.0554 | 0.0408 | 0.1345 | 0.064* | |
H8A | 0.1482 | 0.3915 | 0.3706 | 0.054* | |
H8B | 0.0306 | 0.3094 | 0.4434 | 0.054* | |
H9A | −0.1014 | 0.4874 | 0.3729 | 0.070* | |
H9B | −0.2214 | 0.3867 | 0.3729 | 0.070* | |
H10A | −0.2605 | 0.4062 | 0.1568 | 0.065* | |
H10B | −0.1182 | 0.4964 | 0.1545 | 0.065* | |
H12A | 0.4861 | 0.2380 | 0.1991 | 0.085* | |
H12B | 0.4012 | 0.2376 | 0.3369 | 0.085* | |
H12C | 0.3996 | 0.3406 | 0.2525 | 0.085* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0524 (8) | 0.0509 (7) | 0.0375 (7) | 0.0057 (6) | 0.0117 (6) | 0.0058 (6) |
N1 | 0.0510 (10) | 0.0444 (9) | 0.0404 (9) | −0.0002 (7) | −0.0006 (7) | 0.0079 (7) |
C1 | 0.0587 (13) | 0.0366 (10) | 0.0475 (11) | 0.0085 (9) | 0.0113 (9) | −0.0035 (8) |
C2 | 0.0382 (9) | 0.0395 (9) | 0.0344 (9) | 0.0031 (8) | 0.0044 (7) | 0.0030 (7) |
C3 | 0.0339 (9) | 0.0314 (8) | 0.0337 (9) | 0.0004 (7) | 0.0015 (7) | 0.0043 (7) |
C4 | 0.0391 (10) | 0.0367 (9) | 0.0527 (11) | −0.0046 (8) | 0.0040 (8) | 0.0069 (8) |
C5 | 0.0591 (13) | 0.0360 (10) | 0.0502 (11) | 0.0003 (9) | 0.0122 (9) | 0.0111 (8) |
C6 | 0.0675 (14) | 0.0350 (10) | 0.0558 (12) | 0.0104 (10) | 0.0042 (10) | 0.0103 (9) |
C7 | 0.0680 (14) | 0.0371 (10) | 0.0542 (12) | −0.0133 (9) | −0.0031 (10) | −0.0014 (8) |
C8 | 0.0556 (12) | 0.0417 (10) | 0.0372 (10) | 0.0022 (9) | 0.0072 (8) | 0.0007 (8) |
C9 | 0.0668 (14) | 0.0478 (11) | 0.0615 (13) | 0.0152 (10) | 0.0154 (11) | 0.0012 (9) |
C10 | 0.0504 (12) | 0.0489 (11) | 0.0644 (13) | 0.0096 (10) | 0.0063 (10) | 0.0168 (10) |
C11 | 0.0382 (10) | 0.0370 (9) | 0.0368 (9) | −0.0036 (8) | −0.0025 (8) | 0.0049 (7) |
C12 | 0.0394 (11) | 0.0666 (13) | 0.0629 (13) | 0.0011 (10) | −0.0009 (9) | 0.0071 (10) |
O1—N1 | 1.4269 (19) | C3—C8 | 1.528 (2) |
O1—C2 | 1.479 (2) | C3—C11 | 1.492 (2) |
N1—C11 | 1.269 (2) | C4—C5 | 1.506 (2) |
C1—C2 | 1.541 (2) | C4—C7 | 1.527 (2) |
C1—C6 | 1.512 (3) | C5—C6 | 1.318 (3) |
C1—C7 | 1.528 (3) | C8—C9 | 1.535 (3) |
C2—C3 | 1.543 (2) | C9—C10 | 1.541 (3) |
C2—C12 | 1.505 (3) | C10—C11 | 1.493 (2) |
C3—C4 | 1.570 (2) | ||
N1—O1—C2 | 109.89 (11) | C4—C3—C8 | 114.25 (13) |
O1—N1—C11 | 107.83 (13) | C4—C3—C11 | 114.82 (14) |
C2—C1—C6 | 106.62 (14) | C3—C4—C5 | 104.86 (14) |
C2—C1—C7 | 100.90 (14) | C3—C4—C7 | 101.00 (13) |
C6—C1—C7 | 100.15 (16) | C5—C4—C7 | 100.55 (15) |
O1—C2—C1 | 108.66 (13) | C4—C5—C6 | 107.22 (17) |
O1—C2—C12 | 106.66 (14) | C1—C6—C5 | 107.64 (17) |
C1—C2—C12 | 115.32 (15) | C1—C7—C4 | 93.35 (14) |
O1—C2—C3 | 103.86 (12) | C3—C8—C9 | 104.25 (15) |
C1—C2—C3 | 102.78 (13) | C8—C9—C10 | 107.16 (15) |
C3—C2—C12 | 118.72 (14) | C9—C10—C11 | 102.12 (15) |
C2—C3—C8 | 124.32 (14) | N1—C11—C3 | 116.74 (15) |
C2—C3—C11 | 100.59 (13) | N1—C11—C10 | 129.12 (16) |
C8—C3—C11 | 100.17 (13) | C3—C11—C10 | 112.05 (14) |
C2—C3—C4 | 102.39 (13) | ||
C2—O1—N1—C11 | −9.29 (18) | C7—C4—C5—C6 | 33.84 (19) |
N1—O1—C2—C12 | −115.47 (15) | C3—C4—C5—C6 | −70.64 (18) |
N1—O1—C2—C1 | 119.62 (14) | C4—C5—C6—C1 | −0.2 (2) |
N1—O1—C2—C3 | 10.72 (16) | C7—C1—C6—C5 | −33.45 (19) |
C6—C1—C2—O1 | −175.05 (14) | C2—C1—C6—C5 | 71.3 (2) |
C7—C1—C2—O1 | −70.88 (16) | C5—C4—C7—C1 | −50.59 (15) |
C6—C1—C2—C12 | 65.3 (2) | C3—C4—C7—C1 | 56.98 (15) |
C7—C1—C2—C12 | 169.48 (15) | C6—C1—C7—C4 | 50.21 (15) |
C6—C1—C2—C3 | −65.42 (17) | C2—C1—C7—C4 | −59.08 (15) |
C7—C1—C2—C3 | 38.75 (16) | C11—C3—C8—C9 | 36.73 (17) |
O1—C2—C3—C11 | −7.89 (15) | C2—C3—C8—C9 | 147.12 (16) |
C12—C2—C3—C11 | 110.28 (17) | C4—C3—C8—C9 | −86.54 (17) |
C1—C2—C3—C11 | −121.09 (14) | C3—C8—C9—C10 | −28.7 (2) |
O1—C2—C3—C8 | −118.07 (16) | C8—C9—C10—C11 | 8.0 (2) |
C12—C2—C3—C8 | 0.1 (2) | O1—N1—C11—C3 | 3.7 (2) |
C1—C2—C3—C8 | 128.73 (16) | O1—N1—C11—C10 | 165.83 (18) |
O1—C2—C3—C4 | 110.69 (13) | C8—C3—C11—N1 | 130.97 (16) |
C12—C2—C3—C4 | −131.15 (16) | C2—C3—C11—N1 | 2.93 (19) |
C1—C2—C3—C4 | −2.51 (16) | C4—C3—C11—N1 | −106.16 (17) |
C11—C3—C4—C5 | 177.65 (14) | C8—C3—C11—C10 | −34.13 (18) |
C8—C3—C4—C5 | −67.41 (18) | C2—C3—C11—C10 | −162.17 (15) |
C2—C3—C4—C5 | 69.65 (16) | C4—C3—C11—C10 | 88.74 (18) |
C11—C3—C4—C7 | 73.49 (17) | C9—C10—C11—N1 | −146.04 (19) |
C8—C3—C4—C7 | −171.57 (14) | C9—C10—C11—C3 | 16.7 (2) |
C2—C3—C4—C7 | −34.50 (16) |
Experimental details
Crystal data | |
Chemical formula | C12H15NO |
Mr | 189.25 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 294 |
a, b, c (Å) | 7.640 (2), 12.7121 (14), 10.2205 (7) |
β (°) | 91.668 (11) |
V (Å3) | 992.2 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.08 |
Crystal size (mm) | 0.42 × 0.42 × 0.19 |
Data collection | |
Diffractometer | Enraf-Nonius CAD-4 diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 1997, 1860, 1314 |
Rint | 0.011 |
(sin θ/λ)max (Å−1) | 0.606 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.044, 0.109, 1.04 |
No. of reflections | 1860 |
No. of parameters | 129 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.17, −0.14 |
Computer programs: CAD-4-PC Software (Enraf-Nonius, 1992), SET4 and CELDIM (Enraf-Nonius, 1992), DATRD2 in NRCVAX96 (Gabe et al., 1989), SOLVER in NRCVAX96, NRCVAX96 and SHELXL97 (Sheldrick, 1997), NRCVAX96, SHELXL97 and WORDPERFECT macro PREP8 (Ferguson, 1998).
Recently, we reported the first examples of intramolecular 1,3-dipolar cycloadditions of norbornadiene-tethered nitrile oxides (Yip et al., 1999). Although four different regio- and stereoisomers could be formed in the cycloaddition of 4-(2'-norbornadienyl)butyl nitrile oxide, a single cycloadduct (I) was obtained. The regio- and stereochemistry was established by our single-crystal X-ray diffraction analysis.