2,4-Bis(2-methoxy-phenyl)-3-aza-bicyclo-[3.3.1]nonan-9-one.

In the title compound, C(22)H(25)NO(3), the mol-ecule has a pseudo-mirror plane. The structure is a positional isomer of 2,4-bis(4-methoxy-phenyl)-3-aza-bicyclo-[3.3.1]nonan-9-one [Cox, McCabe, Milne & Sim (1985 ▶). J. Chem. Soc. Chem. Commun. pp. 626-628]. The 3-aza-bicyclo-[3.3.1]nonan-9-one moiety adopts a double chair conformation with equatorial orientations of both 2-methoxy-phenyl substituents on either side of the secondary amino group. The benzene rings are oriented at an angle of 33.86 (4)° with respect to each other and the meth-oxy groups point towards the carbonyl group. The crystal structure is stabilized by intermolecular N-H⋯π inter-actions.

Related literature

For prevalence and biological activities of 3-aza­bicyclo­nonan-9-ones, see: Hardick et al. (1996 ▶); Jeyaraman & Avila (1981 ▶); Barker et al. (2005 ▶). For similiar structures, see: Parthiban et al. (2008a ▶,b ▶); Cox et al. (1985 ▶). For ring-puckering parameters, see: Cremer & Pople (1975 ▶).

Experimental

Crystal data

C22H25NO3

M = 351.43

Monoclinic,

a = 7.8616 (2) Å

b = 20.8443 (6) Å

c = 11.4984 (3) Å

β = 95.670(10)°

V = 1874.37 (9) Å3

Z = 4

Mo Kα radiation

μ = 0.08 mm−1

T = 298 K

0.58 × 0.42 × 0.35 mm

Data collection

Bruker APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 1999 ▶) T min = 0.945, T max = 0.972

14712 measured reflections

4527 independent reflections

3202 reflections with I > 2σ(I)

R int = 0.023

Refinement

R[F 2 > 2σ(F 2)] = 0.048

wR(F 2) = 0.135

S = 1.03

4527 reflections

241 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.17 e Å−3

Δρmin = −0.25 e Å−3

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: APEX2; data reduction: SAINT-Plus (Bruker, 2004 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809018686/bx2207sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809018686/bx2207Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C22H25NO3	F(000) = 752
Mr = 351.43	Dx = 1.245 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 4251 reflections
a = 7.8616 (2) Å	θ = 2.6–27.0°
b = 20.8443 (6) Å	µ = 0.08 mm−1
c = 11.4984 (3) Å	T = 298 K
β = 95.867 (1)°	Block, colourless
V = 1874.37 (9) Å3	0.58 × 0.42 × 0.35 mm
Z = 4

Bruker APEXII CCD area-detector diffractometer	4527 independent reflections
Radiation source: fine-focus sealed tube	3202 reflections with I > 2σ(I)
graphite	Rint = 0.023
φ and ω scans	θmax = 28.3°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 1999)	h = −9→10
Tmin = 0.945, Tmax = 0.972	k = −27→26
14712 measured reflections	l = −15→13

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) = 0.135	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ2(Fo2) + (0.065P)2 + 0.3026P] where P = (Fo2 + 2Fc2)/3
4527 reflections	(Δ/σ)max = 0.001
241 parameters	Δρmax = 0.17 e Å−3
0 restraints	Δρmin = −0.25 e Å−3

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.

	x	y	z	Uiso*/Ueq
C1	0.72892 (16)	0.98913 (6)	0.17176 (12)	0.0343 (3)
H1	0.7974	0.9851	0.1055	0.041*
C2	0.85201 (18)	1.00058 (7)	0.28460 (14)	0.0417 (3)
H2	0.9208	1.0389	0.2735	0.050*
C3	0.7636 (2)	1.00894 (8)	0.39684 (15)	0.0531 (4)
H3A	0.8479	1.0232	0.4589	0.064*
H3B	0.6781	1.0424	0.3840	0.064*
C4	0.6779 (2)	0.94870 (9)	0.43724 (15)	0.0582 (4)
H4A	0.5702	0.9424	0.3894	0.070*
H4B	0.6529	0.9545	0.5175	0.070*
C5	0.7881 (2)	0.88909 (8)	0.42979 (15)	0.0552 (4)
H5A	0.7179	0.8515	0.4390	0.066*
H5B	0.8775	0.8896	0.4945	0.066*
C6	0.87146 (18)	0.88257 (7)	0.31544 (14)	0.0435 (4)
H6	0.9521	0.8466	0.3229	0.052*
C7	0.74651 (17)	0.87292 (6)	0.20328 (13)	0.0366 (3)
H7	0.8145	0.8689	0.1368	0.044*
C8	0.96882 (18)	0.94334 (7)	0.29817 (14)	0.0431 (4)
C9	0.60420 (16)	1.04380 (6)	0.14722 (12)	0.0336 (3)
C10	0.43367 (18)	1.03906 (7)	0.16792 (13)	0.0415 (3)
H10	0.3947	1.0014	0.1994	0.050*
C11	0.32021 (19)	1.08937 (8)	0.14269 (15)	0.0478 (4)
H11	0.2061	1.0851	0.1560	0.057*
C12	0.37750 (19)	1.14550 (7)	0.09793 (14)	0.0467 (4)
H12	0.3019	1.1794	0.0818	0.056*
C13	0.54701 (18)	1.15209 (7)	0.07648 (13)	0.0422 (3)
H13	0.5850	1.1903	0.0462	0.051*
C14	0.65935 (17)	1.10152 (6)	0.10043 (12)	0.0352 (3)
C15	0.63790 (17)	0.81319 (6)	0.20774 (13)	0.0372 (3)
C16	0.69939 (18)	0.75399 (6)	0.17200 (13)	0.0402 (3)
C17	0.5962 (2)	0.69992 (7)	0.16825 (15)	0.0500 (4)
H17	0.6372	0.6609	0.1436	0.060*
C18	0.4323 (2)	0.70404 (8)	0.20125 (16)	0.0547 (4)
H18	0.3631	0.6677	0.1982	0.066*
C19	0.3707 (2)	0.76145 (8)	0.23863 (15)	0.0515 (4)
H19	0.2610	0.7639	0.2618	0.062*
C20	0.47349 (18)	0.81559 (7)	0.24150 (14)	0.0440 (4)
H20	0.4314	0.8543	0.2666	0.053*
C21	0.8836 (2)	1.15648 (10)	0.01693 (18)	0.0661 (5)
H21A	0.8196	1.1579	−0.0587	0.099*
H21B	1.0030	1.1519	0.0079	0.099*
H21C	0.8656	1.1955	0.0583	0.099*
C22	0.9277 (2)	0.69656 (8)	0.09613 (18)	0.0615 (5)
H22A	0.9330	0.6641	0.1556	0.092*
H22B	1.0402	0.7041	0.0736	0.092*
H22C	0.8538	0.6825	0.0293	0.092*
N1	0.63559 (14)	0.92907 (5)	0.18328 (11)	0.0358 (3)
O1	1.12212 (14)	0.94572 (6)	0.29471 (13)	0.0676 (4)
O2	0.82804 (12)	1.10343 (5)	0.08112 (10)	0.0470 (3)
O3	0.86248 (14)	0.75428 (5)	0.14027 (11)	0.0532 (3)
H1A	0.567 (2)	0.9222 (7)	0.1162 (15)	0.046 (4)*

	U11	U22	U33	U12	U13	U23
C1	0.0332 (6)	0.0317 (6)	0.0388 (8)	−0.0012 (5)	0.0068 (6)	−0.0005 (5)
C2	0.0361 (7)	0.0370 (7)	0.0508 (9)	−0.0062 (6)	−0.0013 (6)	−0.0005 (6)
C3	0.0589 (10)	0.0535 (9)	0.0449 (10)	0.0039 (8)	−0.0036 (7)	−0.0115 (7)
C4	0.0631 (11)	0.0733 (12)	0.0390 (9)	−0.0011 (9)	0.0097 (8)	−0.0040 (8)
C5	0.0598 (10)	0.0600 (10)	0.0444 (10)	−0.0077 (8)	−0.0023 (8)	0.0127 (8)
C6	0.0362 (7)	0.0377 (7)	0.0556 (10)	0.0035 (6)	−0.0008 (7)	0.0060 (7)
C7	0.0354 (7)	0.0309 (6)	0.0446 (8)	−0.0010 (5)	0.0093 (6)	0.0003 (6)
C8	0.0344 (7)	0.0488 (8)	0.0448 (9)	−0.0028 (6)	−0.0019 (6)	0.0000 (7)
C9	0.0345 (7)	0.0327 (6)	0.0336 (8)	−0.0008 (5)	0.0029 (5)	−0.0025 (5)
C10	0.0378 (7)	0.0399 (7)	0.0477 (9)	−0.0026 (6)	0.0091 (6)	0.0008 (6)
C11	0.0347 (7)	0.0532 (9)	0.0567 (10)	0.0050 (7)	0.0110 (7)	−0.0022 (8)
C12	0.0453 (8)	0.0438 (8)	0.0507 (10)	0.0126 (7)	0.0038 (7)	−0.0008 (7)
C13	0.0473 (8)	0.0356 (7)	0.0433 (9)	0.0015 (6)	0.0033 (7)	0.0029 (6)
C14	0.0339 (7)	0.0374 (7)	0.0346 (7)	−0.0021 (6)	0.0041 (5)	−0.0008 (6)
C15	0.0397 (7)	0.0348 (7)	0.0371 (8)	−0.0029 (6)	0.0031 (6)	0.0040 (6)
C16	0.0436 (8)	0.0344 (7)	0.0431 (9)	−0.0013 (6)	0.0060 (6)	0.0058 (6)
C17	0.0620 (10)	0.0343 (7)	0.0540 (10)	−0.0063 (7)	0.0073 (8)	0.0020 (7)
C18	0.0591 (10)	0.0470 (9)	0.0577 (11)	−0.0202 (8)	0.0045 (8)	0.0071 (8)
C19	0.0427 (8)	0.0565 (10)	0.0561 (10)	−0.0111 (7)	0.0089 (7)	0.0090 (8)
C20	0.0431 (8)	0.0427 (8)	0.0469 (9)	−0.0021 (6)	0.0086 (7)	0.0025 (7)
C21	0.0463 (9)	0.0827 (13)	0.0698 (13)	−0.0097 (9)	0.0081 (8)	0.0362 (10)
C22	0.0672 (11)	0.0458 (9)	0.0744 (13)	0.0096 (8)	0.0209 (9)	−0.0044 (8)
N1	0.0344 (6)	0.0299 (6)	0.0419 (7)	−0.0020 (5)	−0.0015 (5)	−0.0003 (5)
O1	0.0330 (6)	0.0683 (8)	0.1010 (11)	−0.0040 (5)	0.0034 (6)	0.0059 (7)
O2	0.0359 (5)	0.0468 (6)	0.0593 (7)	−0.0022 (4)	0.0104 (5)	0.0138 (5)
O3	0.0511 (6)	0.0345 (5)	0.0773 (8)	0.0022 (5)	0.0220 (6)	−0.0021 (5)

C1—N1	1.4640 (16)	C11—C12	1.373 (2)
C1—C9	1.5110 (17)	C11—H11	0.9300
C1—C2	1.556 (2)	C12—C13	1.387 (2)
C1—H1	0.9800	C12—H12	0.9300
C2—C8	1.504 (2)	C13—C14	1.3846 (19)
C2—C3	1.537 (2)	C13—H13	0.9300
C2—H2	0.9800	C14—O2	1.3674 (16)
C3—C4	1.520 (2)	C15—C20	1.3879 (19)
C3—H3A	0.9700	C15—C16	1.4021 (19)
C3—H3B	0.9700	C16—O3	1.3684 (17)
C4—C5	1.522 (2)	C16—C17	1.3868 (19)
C4—H4A	0.9700	C17—C18	1.383 (2)
C4—H4B	0.9700	C17—H17	0.9300
C5—C6	1.534 (2)	C18—C19	1.376 (2)
C5—H5A	0.9700	C18—H18	0.9300
C5—H5B	0.9700	C19—C20	1.386 (2)
C6—C8	1.504 (2)	C19—H19	0.9300
C6—C7	1.552 (2)	C20—H20	0.9300
C6—H6	0.9800	C21—O2	1.4227 (18)
C7—N1	1.4636 (16)	C21—H21A	0.9600
C7—C15	1.5136 (17)	C21—H21B	0.9600
C7—H7	0.9800	C21—H21C	0.9600
C8—O1	1.2109 (17)	C22—O3	1.4216 (18)
C9—C10	1.3889 (18)	C22—H22A	0.9600
C9—C14	1.4044 (18)	C22—H22B	0.9600
C10—C11	1.388 (2)	C22—H22C	0.9600
C10—H10	0.9300	N1—H1A	0.907 (17)
N1—C1—C9	109.89 (10)	C11—C10—H10	119.3
N1—C1—C2	109.30 (11)	C9—C10—H10	119.3
C9—C1—C2	112.12 (11)	C12—C11—C10	119.60 (13)
N1—C1—H1	108.5	C12—C11—H11	120.2
C9—C1—H1	108.5	C10—C11—H11	120.2
C2—C1—H1	108.5	C11—C12—C13	120.61 (13)
C8—C2—C3	109.05 (13)	C11—C12—H12	119.7
C8—C2—C1	106.62 (11)	C13—C12—H12	119.7
C3—C2—C1	114.94 (12)	C14—C13—C12	119.63 (13)
C8—C2—H2	108.7	C14—C13—H13	120.2
C3—C2—H2	108.7	C12—C13—H13	120.2
C1—C2—H2	108.7	O2—C14—C13	123.71 (12)
C4—C3—C2	114.56 (13)	O2—C14—C9	115.45 (12)
C4—C3—H3A	108.6	C13—C14—C9	120.84 (12)
C2—C3—H3A	108.6	C20—C15—C16	118.20 (13)
C4—C3—H3B	108.6	C20—C15—C7	121.64 (12)
C2—C3—H3B	108.6	C16—C15—C7	120.09 (12)
H3A—C3—H3B	107.6	O3—C16—C17	123.81 (13)
C3—C4—C5	112.60 (14)	O3—C16—C15	115.77 (12)
C3—C4—H4A	109.1	C17—C16—C15	120.41 (13)
C5—C4—H4A	109.1	C18—C17—C16	119.98 (15)
C3—C4—H4B	109.1	C18—C17—H17	120.0
C5—C4—H4B	109.1	C16—C17—H17	120.0
H4A—C4—H4B	107.8	C19—C18—C17	120.47 (14)
C4—C5—C6	114.58 (13)	C19—C18—H18	119.8
C4—C5—H5A	108.6	C17—C18—H18	119.8
C6—C5—H5A	108.6	C18—C19—C20	119.51 (14)
C4—C5—H5B	108.6	C18—C19—H19	120.2
C6—C5—H5B	108.6	C20—C19—H19	120.2
H5A—C5—H5B	107.6	C19—C20—C15	121.41 (14)
C8—C6—C5	107.83 (13)	C19—C20—H20	119.3
C8—C6—C7	106.67 (12)	C15—C20—H20	119.3
C5—C6—C7	115.74 (12)	O2—C21—H21A	109.5
C8—C6—H6	108.8	O2—C21—H21B	109.5
C5—C6—H6	108.8	H21A—C21—H21B	109.5
C7—C6—H6	108.8	O2—C21—H21C	109.5
N1—C7—C15	109.52 (11)	H21A—C21—H21C	109.5
N1—C7—C6	110.07 (11)	H21B—C21—H21C	109.5
C15—C7—C6	112.93 (11)	O3—C22—H22A	109.5
N1—C7—H7	108.1	O3—C22—H22B	109.5
C15—C7—H7	108.1	H22A—C22—H22B	109.5
C6—C7—H7	108.1	O3—C22—H22C	109.5
O1—C8—C6	124.11 (14)	H22A—C22—H22C	109.5
O1—C8—C2	124.27 (14)	H22B—C22—H22C	109.5
C6—C8—C2	111.62 (12)	C7—N1—C1	113.70 (10)
C10—C9—C14	117.90 (12)	C7—N1—H1A	107.5 (10)
C10—C9—C1	122.25 (12)	C1—N1—H1A	108.7 (10)
C14—C9—C1	119.85 (11)	C14—O2—C21	117.45 (12)
C11—C10—C9	121.42 (13)	C16—O3—C22	118.24 (12)
N1—C1—C2—C8	58.24 (14)	C11—C12—C13—C14	0.0 (2)
C9—C1—C2—C8	−179.66 (11)	C12—C13—C14—O2	179.37 (14)
N1—C1—C2—C3	−62.72 (15)	C12—C13—C14—C9	−0.6 (2)
C9—C1—C2—C3	59.38 (15)	C10—C9—C14—O2	−179.60 (12)
C8—C2—C3—C4	−51.29 (18)	C1—C9—C14—O2	−0.42 (19)
C1—C2—C3—C4	68.33 (18)	C10—C9—C14—C13	0.4 (2)
C2—C3—C4—C5	43.6 (2)	C1—C9—C14—C13	179.54 (13)
C3—C4—C5—C6	−45.3 (2)	N1—C7—C15—C20	−26.68 (19)
C4—C5—C6—C8	54.13 (17)	C6—C7—C15—C20	96.37 (16)
C4—C5—C6—C7	−65.18 (18)	N1—C7—C15—C16	150.24 (13)
C8—C6—C7—N1	−57.03 (14)	C6—C7—C15—C16	−86.71 (16)
C5—C6—C7—N1	62.93 (15)	C20—C15—C16—O3	−179.66 (13)
C8—C6—C7—C15	−179.76 (11)	C7—C15—C16—O3	3.3 (2)
C5—C6—C7—C15	−59.81 (16)	C20—C15—C16—C17	1.4 (2)
C5—C6—C8—O1	117.71 (18)	C7—C15—C16—C17	−175.58 (13)
C7—C6—C8—O1	−117.36 (17)	O3—C16—C17—C18	−179.58 (15)
C5—C6—C8—C2	−62.84 (16)	C15—C16—C17—C18	−0.8 (2)
C7—C6—C8—C2	62.09 (16)	C16—C17—C18—C19	−0.4 (3)
C3—C2—C8—O1	−118.78 (18)	C17—C18—C19—C20	0.9 (3)
C1—C2—C8—O1	116.57 (17)	C18—C19—C20—C15	−0.2 (2)
C3—C2—C8—C6	61.77 (16)	C16—C15—C20—C19	−1.0 (2)
C1—C2—C8—C6	−62.88 (16)	C7—C15—C20—C19	176.01 (14)
N1—C1—C9—C10	17.27 (18)	C15—C7—N1—C1	−177.14 (11)
C2—C1—C9—C10	−104.49 (15)	C6—C7—N1—C1	58.14 (15)
N1—C1—C9—C14	−161.87 (12)	C9—C1—N1—C7	178.03 (11)
C2—C1—C9—C14	76.37 (16)	C2—C1—N1—C7	−58.54 (15)
C14—C9—C10—C11	0.4 (2)	C13—C14—O2—C21	−9.8 (2)
C1—C9—C10—C11	−178.73 (14)	C9—C14—O2—C21	170.19 (14)
C9—C10—C11—C12	−1.0 (2)	C17—C16—O3—C22	2.8 (2)
C10—C11—C12—C13	0.7 (2)	C15—C16—O3—C22	−176.03 (14)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···Cg1i	0.90 (4)	2.75 (4)	3.58 (5)	152.87 (3)

Table 1

N—H⋯π geometry (Å, ° )

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯Cg1i	0.90 (4)	2.75 (4)	3.58 (5)	152.87 (3)

Symmetry code: (i) . Cg1 is the centroid of the C9–C14 ring.