2,2-Dimethyl-5-phenyl-4-oxa-1-aza-6,7:8,9-dibenzobicyclo­[3.2.2]nona­ne

Wang, M.; Xu, J.; Su, W.-P.

doi:10.1107/S1600536807021198

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2,2-Dimethyl-5-phenyl-4-oxa-1-aza-6,7:8,9-dibenzobicyclo[3.2.2]nonane

M. Wang, J. Xu and W.-P. Su

In the title compound, C₂₃H₂₁NO, the six-membered ring of the oxaazabicyclo[3.2.2]nonane unit adopts a boat conformation. One of the seven-membered rings adopts a boat conformation while the other is in a chair conformation. The dihedral angle between the two benzene rings is 51.89 (4)°. There are no hydrogen bonds and the crystal structure is stabilized by van der Waals interactions only.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807021198/ci2373sup1.cif Contains datablocks I, global
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536807021198/ci2373Isup2.hkl Contains datablock I

CCDC reference: 651372

checkCIF report

Key indicators

Single-crystal X-ray study
T = 293 K
Mean (C-C) = 0.002 Å
R factor = 0.048
wR factor = 0.117
Data-to-parameter ratio = 17.3

checkCIF/PLATON results

No syntax errors found



Alert level G
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature .        293 K

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   0 ALERT level C = Check and explain
   2 ALERT level G = General alerts; check

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

Comment top

2-(Trimethylsilyl)phenyltriflate, an efficient precursor to benzyne, has been widely employed for syntheses of complex organic compounds (Pellissier & Santelli, 2003). Recently, Liu and Larock (2004) reported addition of H—X bonds (X = N, O and S) to arynes to construct a new carbon-heteroatom bond (Liu & Larock, 2004). There are also examples of the transition-metal-free insertion of an aryne into polar hetero atom-containing bonds such as C—N σ bond (Yoshida et al., 2002) and intermolecular C—N bond reaction under very mild conditions (Liu & Larock, 2005). However, there is no example of insertion of aryne into C═N double bonds. We report here the crystal structure of the title compound, (I), which was obtained through insertion of two benzyne molecules into C═N double bonds.

As shown in Fig. 1, the oxaazabicyclo[3.2.2]nonane unit is composed of one six-membered ring and two seven-membered rings, which are connected with each other by the brigdehead atoms N1 and C7. The bond lengths and angles in (I) are normal except the slightly longer C7—C23 [1.5296 (19) Å], C7—C17 [1.5317 (19) Å] and C9—N1 [1.5209 (18) Å] bonds, which may result from the ring fusion.

The six-membered ring of the oxaazabicyclo[3.2.2]nonane unit adopts a boat conformation, with atoms N1 and C7 deviating from the C12/C17/C18/C23 plane by 0.542 (1) and 0.608 (1) Å, respectively. One of the seven-membered rings (N1,C9,C8,O1,C7,C23,C18) adopts a boat conformation, with atoms C8, C18 and C23 deviating from the plane defined by other four atoms by 0.624 (2), 1.149 (1) and 1.249 (1) Å, respectively. The other seven-membered ring (N1,C9,C8,O1,C7,C12,C17) adopts a chair conformation. The dihedral angle between the two benzene rings (C12—C17 and C18—C23) is 51.89 (4)°. The C1—C6 phenyl ring forms dihedral angles of 60.04 (5)° and 68.23 (5)°, respectively, with the C12—C17 and C18—C23 benzene rings.

No significant hydrogen bonds are observed in the crystal structure.

Related literature top

For general background, see: Liu & Larock (2004, 2005); Pellissier & Santelli (2003); Yoshida et al. (2002).

Experimental top

2-(Trimethylsilyl)phenyl trifluoromethanesulfonate (0.48 ml) and 4,4-dimethyl-2-oxazoline (0.12 ml) were added to a mixture of CsF (0.3032 g), [RuCl₂(η⁶-C₆H₆)]₂ (0.02 g), PPh₃ (0.042 g) in CH₃CN (0.6 ml) and toluene (3.0 ml). The mixture was stirred under argon at 408 K for 24 h. The organic layer was filtered and concentrated in vacuo. The crude product was further purified by column chromatography on silica gel to obtain the title compound as a white solid. Colourless needle-shaped crystals of (I) suitable for X-ray analysis were grown by slow evaporation of a hexane solution at room temperature.

Structure description top

No significant hydrogen bonds are observed in the crystal structure.

For general background, see: Liu & Larock (2004, 2005); Pellissier & Santelli (2003); Yoshida et al. (2002).

Computing details top

Data collection: CrystalClear (Rigaku/MSC, 2004); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXTL (Sheldrick, 1997); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures top

Fig. 1. The molecular structure of (I), showing 30% probability displacement ellopsoids. H atoms have been omitted for clarity.

2,2-Dimethyl-5-phenyl-4-oxa-1-aza-6,7:8,9-dibenzobicyclo[3.2.2]nonane top

Crystal data top

C₂₃H₂₁NO	F(000) = 696
M_r = 327.41	D_x = 1.256 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3669 reflections
a = 15.707 (6) Å	θ = 2.8–27.5°
b = 9.227 (4) Å	µ = 0.08 mm⁻¹
c = 12.198 (5) Å	T = 293 K
β = 101.575 (6)°	Prism, colourless
V = 1731.7 (12) Å³	0.20 × 0.15 × 0.11 mm
Z = 4

Data collection top

Rigaku Mercury CCD area-detector diffractometer	3911 independent reflections
Radiation source: fine-focus sealed tube	3171 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.033
Detector resolution: 14.6306 pixels mm^-1	θ_max = 27.4°, θ_min = 2.8°
ω scans	h = −18→20
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2004)	k = −11→11
T_min = 0.981, T_max = 0.992	l = −15→15
13049 measured reflections

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)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.117	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.0498P)² + 0.3898P] where P = (F_o² + 2F_c²)/3
3911 reflections	(Δ/σ)_max = 0.001
226 parameters	Δρ_max = 0.21 e Å⁻³
0 restraints	Δρ_min = −0.17 e Å⁻³

Crystal data top

C₂₃H₂₁NO	V = 1731.7 (12) Å³
M_r = 327.41	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 15.707 (6) Å	µ = 0.08 mm⁻¹
b = 9.227 (4) Å	T = 293 K
c = 12.198 (5) Å	0.20 × 0.15 × 0.11 mm
β = 101.575 (6)°

Data collection top

Rigaku Mercury CCD area-detector diffractometer	3911 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2004)	3171 reflections with I > 2σ(I)
T_min = 0.981, T_max = 0.992	R_int = 0.033
13049 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.048	0 restraints
wR(F²) = 0.117	H-atom parameters constrained
S = 1.07	Δρ_max = 0.21 e Å⁻³
3911 reflections	Δρ_min = −0.17 e Å⁻³
226 parameters

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	U_iso*/U_eq
C1	0.96183 (10)	0.24037 (17)	0.28052 (13)	0.0431 (4)
H1	0.9429	0.2047	0.3428	0.052*
C2	1.04785 (10)	0.28135 (19)	0.28977 (15)	0.0519 (4)
H2	1.0861	0.2729	0.3583	0.062*
C3	1.07728 (10)	0.33424 (19)	0.19895 (16)	0.0532 (4)
H3	1.1348	0.3634	0.2061	0.064*
C4	1.02079 (11)	0.34364 (19)	0.09715 (16)	0.0532 (4)
H4	1.0406	0.3769	0.0348	0.064*
C5	0.93473 (10)	0.30390 (19)	0.08725 (13)	0.0464 (4)
H5	0.8969	0.3118	0.0183	0.056*
C6	0.90390 (9)	0.25219 (15)	0.17922 (11)	0.0347 (3)
C7	0.80819 (9)	0.21735 (15)	0.16881 (10)	0.0317 (3)
C8	0.72086 (9)	0.18203 (16)	0.31426 (11)	0.0355 (3)
H8A	0.7166	0.2861	0.3229	0.043*
H8B	0.7257	0.1387	0.3877	0.043*
C9	0.63664 (9)	0.12763 (15)	0.23859 (11)	0.0343 (3)
C10	0.56008 (10)	0.19291 (19)	0.28076 (13)	0.0473 (4)
H10A	0.5067	0.1602	0.2346	0.071*
H10B	0.5630	0.2967	0.2776	0.071*
H10C	0.5623	0.1629	0.3567	0.071*
C11	0.63202 (12)	−0.03686 (17)	0.24199 (14)	0.0484 (4)
H11A	0.5791	−0.0691	0.1944	0.073*
H11B	0.6332	−0.0680	0.3174	0.073*
H11C	0.6808	−0.0773	0.2163	0.073*
C12	0.68217 (9)	0.08999 (14)	0.05706 (11)	0.0327 (3)
C13	0.64116 (11)	−0.00665 (16)	−0.02287 (12)	0.0411 (3)
H13	0.5811	−0.0174	−0.0360	0.049*
C14	0.69024 (12)	−0.08768 (17)	−0.08352 (13)	0.0490 (4)
H14	0.6629	−0.1526	−0.1376	0.059*
C15	0.77895 (12)	−0.07215 (18)	−0.06376 (13)	0.0499 (4)
H15	0.8115	−0.1270	−0.1044	0.060*
C16	0.82047 (10)	0.02507 (16)	0.01655 (12)	0.0411 (3)
H16	0.8806	0.0349	0.0296	0.049*
C17	0.77218 (9)	0.10735 (14)	0.07715 (11)	0.0323 (3)
C18	0.66150 (9)	0.32615 (14)	0.11765 (10)	0.0308 (3)
C19	0.60351 (10)	0.44013 (16)	0.09311 (12)	0.0389 (3)
H19	0.5440	0.4225	0.0772	0.047*
C20	0.63460 (11)	0.58057 (17)	0.09236 (13)	0.0449 (4)
H20	0.5958	0.6573	0.0751	0.054*
C21	0.72252 (11)	0.60710 (17)	0.11705 (13)	0.0452 (4)
H21	0.7430	0.7016	0.1158	0.054*
C22	0.78091 (10)	0.49345 (15)	0.14383 (12)	0.0381 (3)
H22	0.8402	0.5122	0.1622	0.046*
C23	0.75088 (9)	0.35205 (14)	0.14324 (10)	0.0307 (3)
O1	0.79830 (6)	0.15078 (11)	0.27410 (7)	0.0358 (2)
N1	0.63133 (7)	0.17812 (12)	0.11871 (9)	0.0325 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0368 (8)	0.0491 (9)	0.0415 (8)	−0.0009 (7)	0.0032 (6)	−0.0013 (7)
C2	0.0377 (9)	0.0570 (10)	0.0559 (10)	−0.0020 (7)	−0.0031 (7)	−0.0066 (8)
C3	0.0332 (8)	0.0485 (10)	0.0780 (12)	−0.0036 (7)	0.0117 (8)	−0.0092 (9)
C4	0.0452 (9)	0.0560 (10)	0.0637 (11)	−0.0010 (8)	0.0238 (8)	0.0047 (8)
C5	0.0375 (8)	0.0608 (10)	0.0419 (8)	0.0017 (7)	0.0100 (6)	0.0058 (7)
C6	0.0312 (7)	0.0361 (7)	0.0368 (7)	0.0039 (6)	0.0066 (6)	−0.0011 (6)
C7	0.0326 (7)	0.0355 (7)	0.0267 (6)	0.0028 (6)	0.0054 (5)	0.0024 (5)
C8	0.0373 (8)	0.0425 (8)	0.0279 (6)	0.0018 (6)	0.0094 (5)	0.0018 (6)
C9	0.0353 (7)	0.0369 (7)	0.0317 (7)	−0.0009 (6)	0.0089 (6)	0.0008 (6)
C10	0.0401 (8)	0.0591 (10)	0.0453 (9)	0.0001 (7)	0.0152 (7)	−0.0017 (7)
C11	0.0598 (10)	0.0403 (9)	0.0468 (9)	−0.0079 (7)	0.0150 (8)	0.0049 (7)
C12	0.0391 (7)	0.0307 (7)	0.0279 (6)	0.0021 (6)	0.0059 (5)	0.0009 (5)
C13	0.0486 (9)	0.0373 (8)	0.0353 (7)	−0.0030 (7)	0.0032 (6)	−0.0026 (6)
C14	0.0700 (12)	0.0368 (8)	0.0377 (8)	0.0021 (8)	0.0049 (7)	−0.0088 (6)
C15	0.0684 (11)	0.0413 (9)	0.0421 (9)	0.0147 (8)	0.0163 (8)	−0.0050 (7)
C16	0.0449 (8)	0.0401 (8)	0.0395 (8)	0.0095 (7)	0.0114 (6)	0.0016 (6)
C17	0.0382 (7)	0.0310 (7)	0.0276 (6)	0.0049 (6)	0.0060 (5)	0.0033 (5)
C18	0.0341 (7)	0.0312 (7)	0.0265 (6)	0.0021 (5)	0.0045 (5)	−0.0003 (5)
C19	0.0354 (7)	0.0420 (8)	0.0376 (7)	0.0075 (6)	0.0036 (6)	0.0013 (6)
C20	0.0501 (9)	0.0358 (8)	0.0476 (9)	0.0116 (7)	0.0069 (7)	0.0037 (6)
C21	0.0544 (10)	0.0315 (8)	0.0496 (9)	−0.0003 (7)	0.0106 (7)	0.0019 (6)
C22	0.0390 (8)	0.0365 (8)	0.0388 (8)	−0.0022 (6)	0.0081 (6)	−0.0002 (6)
C23	0.0328 (7)	0.0331 (7)	0.0260 (6)	0.0015 (5)	0.0050 (5)	−0.0004 (5)
O1	0.0330 (5)	0.0443 (6)	0.0305 (5)	0.0051 (4)	0.0075 (4)	0.0069 (4)
N1	0.0340 (6)	0.0326 (6)	0.0305 (6)	0.0001 (5)	0.0058 (5)	−0.0019 (5)

Geometric parameters (Å, º) top

C1—C6	1.384 (2)	C11—H11A	0.96
C1—C2	1.386 (2)	C11—H11B	0.96
C1—H1	0.93	C11—H11C	0.96
C2—C3	1.373 (3)	C12—C13	1.381 (2)
C2—H2	0.93	C12—C17	1.395 (2)
C3—C4	1.376 (3)	C12—N1	1.4510 (17)
C3—H3	0.93	C13—C14	1.389 (2)
C4—C5	1.382 (2)	C13—H13	0.93
C4—H4	0.93	C14—C15	1.373 (2)
C5—C6	1.392 (2)	C14—H14	0.93
C5—H5	0.93	C15—C16	1.390 (2)
C6—C7	1.518 (2)	C15—H15	0.93
C7—O1	1.4596 (16)	C16—C17	1.3868 (19)
C7—C23	1.5296 (19)	C16—H16	0.93
C7—C17	1.5317 (19)	C18—C19	1.384 (2)
C8—O1	1.4289 (16)	C18—C23	1.3963 (19)
C8—C9	1.537 (2)	C18—N1	1.4467 (18)
C8—H8A	0.97	C19—C20	1.385 (2)
C8—H8B	0.97	C19—H19	0.93
C9—C11	1.520 (2)	C20—C21	1.375 (2)
C9—N1	1.5209 (18)	C20—H20	0.93
C9—C10	1.524 (2)	C21—C22	1.388 (2)
C10—H10A	0.96	C21—H21	0.93
C10—H10B	0.96	C22—C23	1.387 (2)
C10—H10C	0.96	C22—H22	0.93

C6—C1—C2	120.45 (15)	H11A—C11—H11B	109.5
C6—C1—H1	119.8	C9—C11—H11C	109.5
C2—C1—H1	119.8	H11A—C11—H11C	109.5
C3—C2—C1	120.80 (16)	H11B—C11—H11C	109.5
C3—C2—H2	119.6	C13—C12—C17	120.72 (13)
C1—C2—H2	119.6	C13—C12—N1	120.02 (13)
C2—C3—C4	119.33 (15)	C17—C12—N1	119.24 (12)
C2—C3—H3	120.3	C12—C13—C14	119.55 (15)
C4—C3—H3	120.3	C12—C13—H13	120.2
C3—C4—C5	120.28 (16)	C14—C13—H13	120.2
C3—C4—H4	119.9	C15—C14—C13	120.16 (15)
C5—C4—H4	119.9	C15—C14—H14	119.9
C4—C5—C6	120.84 (15)	C13—C14—H14	119.9
C4—C5—H5	119.6	C14—C15—C16	120.47 (14)
C6—C5—H5	119.6	C14—C15—H15	119.8
C1—C6—C5	118.27 (14)	C16—C15—H15	119.8
C1—C6—C7	121.39 (13)	C17—C16—C15	119.95 (15)
C5—C6—C7	120.27 (12)	C17—C16—H16	120.0
O1—C7—C6	107.10 (10)	C15—C16—H16	120.0
O1—C7—C23	111.05 (10)	C16—C17—C12	119.14 (13)
C6—C7—C23	112.18 (11)	C16—C17—C7	126.19 (13)
O1—C7—C17	105.93 (11)	C12—C17—C7	114.66 (11)
C6—C7—C17	114.58 (11)	C19—C18—C23	120.45 (13)
C23—C7—C17	105.87 (10)	C19—C18—N1	121.12 (13)
O1—C8—C9	114.67 (11)	C23—C18—N1	118.43 (11)
O1—C8—H8A	108.6	C18—C19—C20	119.65 (14)
C9—C8—H8A	108.6	C18—C19—H19	120.2
O1—C8—H8B	108.6	C20—C19—H19	120.2
C9—C8—H8B	108.6	C21—C20—C19	120.32 (14)
H8A—C8—H8B	107.6	C21—C20—H20	119.8
C11—C9—N1	109.77 (11)	C19—C20—H20	119.8
C11—C9—C10	109.89 (12)	C20—C21—C22	120.27 (14)
N1—C9—C10	107.99 (11)	C20—C21—H21	119.9
C11—C9—C8	110.46 (12)	C22—C21—H21	119.9
N1—C9—C8	110.59 (11)	C23—C22—C21	120.09 (14)
C10—C9—C8	108.09 (12)	C23—C22—H22	120.0
C9—C10—H10A	109.5	C21—C22—H22	120.0
C9—C10—H10B	109.5	C22—C23—C18	119.20 (12)
H10A—C10—H10B	109.5	C22—C23—C7	125.29 (13)
C9—C10—H10C	109.5	C18—C23—C7	115.51 (12)
H10A—C10—H10C	109.5	C8—O1—C7	117.70 (10)
H10B—C10—H10C	109.5	C18—N1—C12	108.01 (11)
C9—C11—H11A	109.5	C18—N1—C9	110.05 (10)
C9—C11—H11B	109.5	C12—N1—C9	113.39 (10)

Experimental details

Crystal data
Chemical formula	C₂₃H₂₁NO
M_r	327.41
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	15.707 (6), 9.227 (4), 12.198 (5)
β (°)	101.575 (6)
V (Å³)	1731.7 (12)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.20 × 0.15 × 0.11

Data collection
Diffractometer	Rigaku Mercury CCD area-detector
Absorption correction	Multi-scan (CrystalClear; Rigaku/MSC, 2004)
T_min, T_max	0.981, 0.992
No. of measured, independent and observed [I > 2σ(I)] reflections	13049, 3911, 3171
R_int	0.033
(sin θ/λ)_max (Å⁻¹)	0.648

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.048, 0.117, 1.07
No. of reflections	3911
No. of parameters	226
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.21, −0.17

Computer programs: CrystalClear (Rigaku/MSC, 2004), CrystalClear, SHELXTL (Sheldrick, 1997), SHELXTL.

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