2,3,3a,4,5a,6,7,8-Octa­hydro-5a-methyl-6,9-methano-1H,9H-5-oxa-4-aza­cyclo­penta­[c]­indene

The regio- and stereochemistry of the title compound, C₁₂H₁₅NO, has been established by X-ray analysis. The molecular dimensions are normal.

S1. Comment

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.

S2. Experimental

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.

S3. Refinement

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).

Computing details

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).

2,3,3a,4,5a,6,7,8-Octahydro-5a-methyl-6,9-methano-1H,9H-5-oxa-4-azacyclo- penta[c]indene

Crystal data

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) Å^3	Plate, colorless
Z = 4	0.42 × 0.42 × 0.19 mm
F(000) = 408

Data collection

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

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.044	H-atom parameters constrained
wR(F^2) = 0.109	w = 1/[σ^2(Fo^2) + (0.0523P)^2 + 0.076P] where P = (Fo^2 + 2Fc^2)/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+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.103 (7)

Special details

Experimental. ? #Insert any special details here.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	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*

Atomic displacement parameters (Ų)

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

Geometric parameters (Å, º)

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)