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).
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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.