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The structure of the adduct of eucarvone with nitrosobenzene, C
16H
19NO
2, is reported. The [3.2.2] bicyclic system corresponds to two seven-membered rings in boat and distorted chair conformations and a six-membered ring that adopts a distorted boat conformation. No conjugation is observed between the phenyl group and the N-O system. The packing is directed mainly by a C
O hydrogen bond, C-H
O-(1 -
x, -
y, z) and by intermolecular C-H
interactions.
Supporting information
CCDC reference: 146049
Data collection: MSC/AFC Diffractometer Software (Molecular Structure Corporation, 1993); cell refinement: MSC/AFC Diffractometer Software; data reduction: MSC/AFC Diffractometer Software; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ZORTEP (Zsolnai & Pritzkow, 1995); software used to prepare material for publication: PLATON (Spek, 1990) and CSD (Allen & Kennard, 1993).
N-Phenyl-8-oxa-9-aza-1,4,4-trimethylbicyclo[3.2.2]non-6-en-one
top
Crystal data top
C16H19NO2 | Dx = 1.205 Mg m−3 |
Mr = 257.32 | Melting point: 329-331 K K |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71069 Å |
a = 10.417 (3) Å | Cell parameters from 25 reflections |
b = 8.263 (2) Å | θ = 20.2–25.4° |
c = 16.5049 (12) Å | µ = 0.08 mm−1 |
β = 92.746 (11)° | T = 293 K |
V = 1419.0 (5) Å3 | Prismatic, colourless |
Z = 4 | 0.20 × 0.17 × 0.13 mm |
F(000) = 552 | |
Data collection top
Rigaku AFC7S diffractometer | 1819 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.017 |
Graphite monochromator | θmax = 27.5°, θmin = 2.3° |
θ/2θ scans | h = −7→13 |
Absorption correction: ψ scan MSC/AFC Diffractometer Software (Molecular Structure Corporation, 1993) | k = −8→10 |
Tmin = 0.964, Tmax = 1.000 | l = −21→21 |
3571 measured reflections | 3 standard reflections every 150 reflections |
3254 independent reflections | intensity decay: none |
Refinement top
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)] = 0.042 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.139 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0692P)2 + 0.0281P] where P = (Fo2 + 2Fc2)/3 |
3254 reflections | (Δ/σ)max < 0.001 |
230 parameters | Δρmax = 0.15 e Å−3 |
0 restraints | Δρmin = −0.18 e Å−3 |
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 | x | y | z | Uiso*/Ueq | |
O8 | 0.26910 (10) | 0.14764 (15) | 0.17573 (6) | 0.0477 (3) | |
N9 | 0.14840 (12) | 0.22317 (17) | 0.15069 (8) | 0.0420 (3) | |
C5 | 0.14606 (15) | 0.2695 (2) | 0.06363 (10) | 0.0427 (4) | |
H5 | 0.0550 (19) | 0.308 (3) | 0.0517 (13) | 0.0768 (15)* | |
C1' | 0.04377 (14) | 0.1178 (2) | 0.16876 (9) | 0.0412 (4) | |
C6 | 0.17444 (16) | 0.1237 (2) | 0.01383 (10) | 0.0470 (4) | |
H6 | 0.116 (2) | 0.092 (3) | −0.0327 (13) | 0.0768 (15)* | |
C6' | 0.05857 (18) | −0.0423 (2) | 0.19187 (11) | 0.0516 (4) | |
H6' | 0.139 (2) | −0.091 (3) | 0.1937 (13) | 0.0768 (15)* | |
C3 | 0.36929 (17) | 0.3970 (2) | 0.09007 (13) | 0.0526 (5) | |
H3A | 0.426 (2) | 0.478 (3) | 0.0650 (13) | 0.0768 (15)* | |
H3B | 0.363 (2) | 0.421 (3) | 0.1489 (14) | 0.0768 (15)* | |
C2' | −0.07857 (17) | 0.1854 (2) | 0.16498 (12) | 0.0537 (5) | |
H2' | −0.0897 (19) | 0.296 (3) | 0.1513 (13) | 0.0768 (15)* | |
C4 | 0.23284 (16) | 0.4181 (2) | 0.05003 (11) | 0.0486 (4) | |
C2 | 0.42900 (16) | 0.2330 (2) | 0.08382 (11) | 0.0514 (4) | |
O21 | 0.53526 (12) | 0.2135 (2) | 0.05849 (11) | 0.0804 (5) | |
C1 | 0.35052 (15) | 0.0881 (2) | 0.11205 (11) | 0.0480 (4) | |
C7 | 0.27174 (17) | 0.0326 (2) | 0.03874 (11) | 0.0502 (4) | |
H7 | 0.297 (2) | −0.059 (3) | 0.0125 (14) | 0.0768 (15)* | |
C4' | −0.1701 (2) | −0.0671 (3) | 0.20375 (12) | 0.0633 (6) | |
H4' | −0.249 (2) | −0.126 (3) | 0.2149 (13) | 0.0768 (15)* | |
C5' | −0.0494 (2) | −0.1331 (3) | 0.20905 (13) | 0.0633 (5) | |
H5' | −0.038 (2) | −0.246 (3) | 0.2252 (14) | 0.0768 (15)* | |
C3' | −0.18474 (19) | 0.0929 (3) | 0.18087 (13) | 0.0625 (5) | |
H3' | −0.273 (2) | 0.146 (3) | 0.1785 (13) | 0.0768 (15)* | |
C11 | 0.4341 (2) | −0.0420 (3) | 0.15148 (17) | 0.0682 (6) | |
H11A | 0.381 (2) | −0.131 (3) | 0.1656 (13) | 0.0768 (15)* | |
H11B | 0.482 (2) | 0.001 (3) | 0.2009 (14) | 0.0768 (15)* | |
H11C | 0.503 (2) | −0.077 (3) | 0.1149 (13) | 0.0768 (15)* | |
C41 | 0.1732 (2) | 0.5678 (3) | 0.08779 (18) | 0.0715 (6) | |
H41A | 0.159 (2) | 0.552 (3) | 0.1470 (15) | 0.0768 (15)* | |
H41B | 0.232 (2) | 0.662 (3) | 0.0817 (13) | 0.0768 (15)* | |
H41C | 0.088 (2) | 0.589 (3) | 0.0615 (13) | 0.0768 (15)* | |
C42 | 0.2427 (2) | 0.4429 (3) | −0.04122 (14) | 0.0689 (6) | |
H42A | 0.154 (2) | 0.452 (3) | −0.0690 (14) | 0.0768 (15)* | |
H42B | 0.281 (2) | 0.545 (3) | −0.0495 (13) | 0.0768 (15)* | |
H42C | 0.296 (2) | 0.349 (3) | −0.0651 (14) | 0.0768 (15)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O8 | 0.0402 (6) | 0.0591 (7) | 0.0434 (6) | 0.0040 (5) | −0.0035 (5) | 0.0027 (5) |
N9 | 0.0381 (7) | 0.0443 (7) | 0.0437 (7) | 0.0021 (6) | 0.0023 (5) | 0.0016 (6) |
C5 | 0.0391 (8) | 0.0448 (9) | 0.0440 (9) | −0.0001 (7) | −0.0008 (6) | 0.0068 (7) |
C1' | 0.0432 (9) | 0.0446 (9) | 0.0361 (8) | −0.0013 (7) | 0.0045 (6) | −0.0032 (7) |
C6 | 0.0467 (9) | 0.0532 (10) | 0.0411 (9) | −0.0096 (8) | 0.0034 (7) | −0.0002 (8) |
C6' | 0.0523 (10) | 0.0535 (11) | 0.0491 (10) | 0.0020 (9) | 0.0022 (8) | 0.0094 (8) |
C3 | 0.0448 (10) | 0.0465 (10) | 0.0661 (12) | −0.0069 (8) | −0.0001 (8) | 0.0016 (9) |
C2' | 0.0481 (10) | 0.0511 (11) | 0.0631 (11) | 0.0037 (9) | 0.0136 (8) | −0.0010 (9) |
C4 | 0.0440 (9) | 0.0433 (9) | 0.0583 (11) | −0.0030 (7) | 0.0010 (7) | 0.0080 (8) |
C2 | 0.0391 (9) | 0.0576 (11) | 0.0572 (11) | −0.0006 (8) | −0.0011 (7) | −0.0040 (9) |
O21 | 0.0453 (8) | 0.0803 (10) | 0.1174 (13) | −0.0002 (7) | 0.0243 (8) | −0.0069 (9) |
C1 | 0.0390 (8) | 0.0460 (9) | 0.0592 (10) | 0.0051 (7) | 0.0041 (7) | −0.0012 (8) |
C7 | 0.0544 (10) | 0.0438 (9) | 0.0529 (10) | −0.0030 (8) | 0.0095 (8) | −0.0090 (8) |
C4' | 0.0604 (12) | 0.0739 (15) | 0.0565 (11) | −0.0176 (11) | 0.0115 (9) | 0.0068 (10) |
C5' | 0.0714 (13) | 0.0566 (12) | 0.0619 (12) | −0.0112 (10) | 0.0032 (10) | 0.0174 (10) |
C3' | 0.0486 (10) | 0.0744 (14) | 0.0657 (12) | −0.0007 (10) | 0.0139 (9) | −0.0042 (11) |
C11 | 0.0535 (12) | 0.0578 (13) | 0.0923 (16) | 0.0126 (10) | −0.0077 (11) | 0.0071 (12) |
C41 | 0.0610 (13) | 0.0437 (12) | 0.110 (2) | 0.0040 (10) | 0.0060 (13) | 0.0071 (12) |
C42 | 0.0644 (13) | 0.0709 (15) | 0.0711 (14) | −0.0150 (11) | −0.0021 (10) | 0.0257 (12) |
Geometric parameters (Å, º) top
O8—N9 | 1.4461 (17) | C3—C4 | 1.548 (2) |
O8—C1 | 1.4669 (19) | C2'—C3' | 1.380 (3) |
N9—C1' | 1.437 (2) | C4—C42 | 1.528 (3) |
N9—C5 | 1.486 (2) | C4—C41 | 1.531 (3) |
C5—C6 | 1.496 (2) | C2—O21 | 1.213 (2) |
C5—C4 | 1.547 (2) | C2—C1 | 1.535 (3) |
C1'—C6' | 1.383 (2) | C1—C7 | 1.501 (3) |
C1'—C2' | 1.390 (2) | C1—C11 | 1.511 (3) |
C6—C7 | 1.313 (3) | C4'—C5' | 1.370 (3) |
C6'—C5' | 1.392 (3) | C4'—C3' | 1.381 (3) |
C3—C2 | 1.497 (3) | | |
| | | |
N9—O8—C1 | 117.69 (11) | C42—C4—C3 | 109.39 (16) |
C1'—N9—O8 | 109.68 (12) | C41—C4—C3 | 107.44 (17) |
C1'—N9—C5 | 112.29 (12) | C5—C4—C3 | 112.31 (14) |
O8—N9—C5 | 111.19 (11) | O21—C2—C3 | 122.22 (17) |
N9—C5—C6 | 109.20 (13) | O21—C2—C1 | 120.62 (17) |
N9—C5—C4 | 111.23 (13) | C3—C2—C1 | 117.15 (14) |
C6—C5—C4 | 115.28 (13) | O8—C1—C7 | 111.57 (13) |
C6'—C1'—C2' | 119.11 (16) | O8—C1—C11 | 105.74 (16) |
C6'—C1'—N9 | 124.11 (15) | C7—C1—C11 | 114.30 (17) |
C2'—C1'—N9 | 116.74 (15) | O8—C1—C2 | 106.88 (13) |
C7—C6—C5 | 117.38 (16) | C7—C1—C2 | 105.79 (14) |
C1'—C6'—C5' | 119.41 (18) | C11—C1—C2 | 112.42 (15) |
C2—C3—C4 | 116.65 (15) | C6—C7—C1 | 117.48 (17) |
C3'—C2'—C1' | 120.68 (19) | C5'—C4'—C3' | 119.16 (19) |
C42—C4—C41 | 109.90 (18) | C4'—C5'—C6' | 121.4 (2) |
C42—C4—C5 | 108.47 (15) | C2'—C3'—C4' | 120.2 (2) |
C41—C4—C5 | 109.31 (15) | | |
| | | |
C1—O8—N9—C1' | 108.11 (14) | C2—C3—C4—C42 | −80.2 (2) |
C1—O8—N9—C5 | −16.70 (18) | C2—C3—C4—C41 | 160.50 (17) |
C1'—N9—C5—C6 | −68.04 (17) | C2—C3—C4—C5 | 40.3 (2) |
O8—N9—C5—C6 | 55.29 (16) | C4—C3—C2—O21 | 127.8 (2) |
C1'—N9—C5—C4 | 163.61 (13) | C4—C3—C2—C1 | −53.0 (2) |
O8—N9—C5—C4 | −73.06 (16) | N9—O8—C1—C7 | −31.29 (19) |
O8—N9—C1'—C6' | −11.4 (2) | N9—O8—C1—C11 | −156.12 (14) |
C5—N9—C1'—C6' | 112.80 (17) | N9—O8—C1—C2 | 83.91 (15) |
O8—N9—C1'—C2' | 166.40 (14) | O21—C2—C1—O8 | 149.90 (18) |
C5—N9—C1'—C2' | −69.43 (18) | C3—C2—C1—O8 | −29.4 (2) |
N9—C5—C6—C7 | −46.37 (19) | O21—C2—C1—C7 | −91.1 (2) |
C4—C5—C6—C7 | 79.7 (2) | C3—C2—C1—C7 | 89.66 (19) |
C2'—C1'—C6'—C5' | 1.4 (3) | O21—C2—C1—C11 | 34.3 (3) |
N9—C1'—C6'—C5' | 179.14 (16) | C3—C2—C1—C11 | −144.93 (19) |
C6'—C1'—C2'—C3' | −2.6 (3) | C5—C6—C7—C1 | −3.5 (2) |
N9—C1'—C2'—C3' | 179.56 (17) | O8—C1—C7—C6 | 43.1 (2) |
N9—C5—C4—C42 | 171.28 (15) | C11—C1—C7—C6 | 163.04 (18) |
C6—C5—C4—C42 | 46.3 (2) | C2—C1—C7—C6 | −72.72 (19) |
N9—C5—C4—C41 | −68.9 (2) | C3'—C4'—C5'—C6' | 0.0 (3) |
C6—C5—C4—C41 | 166.10 (17) | C1'—C6'—C5'—C4' | −0.2 (3) |
N9—C5—C4—C3 | 50.25 (19) | C1'—C2'—C3'—C4' | 2.4 (3) |
C6—C5—C4—C3 | −74.76 (19) | C5'—C4'—C3'—C2' | −1.1 (3) |
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