1,4,4-Tri­methyl-9-phenyl-8-oxa-9-aza­bi­cyclo­[3.2.2]­non-6-en-2-one

The structure of the adduct of eucarvone with nitro­so­benzene, C₁₆H₁₉NO₂, 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...[pi] interactions.

Computing details

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

Crystal data

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) Å^3	Prismatic, colourless
Z = 4	0.20 × 0.17 × 0.13 mm
F(000) = 552

Data collection

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

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.139	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0692P)^2 + 0.0281P] where P = (Fo^2 + 2Fc^2)/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

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 (Ų)

	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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

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)