2,4-Bis(4-eth-oxy-phen-yl)-1-methyl-3-aza-bicyclo-[3.3.1]nonan-9-one.

In the title compound, C(25)H(30)NO(3), a crystallographic mirror plane bis-ects the mol-ecule. Although it is a positional isomer of 2,4-bis(4-eth-oxy-phen-yl)-7-methyl-3-aza-bicyclo-[3.3.1]non-an-9-one [C(25)H(31)NO(3), M(r) = 393.51; Park et al. (2012c ▶). Acta Cryst. E68, o779-780], its mol-ecular weight is 392.50 due to the 50:50 ratio of the methyl group at bridgehead C atoms. However, the title compound exists in the same twin-chair conformation as its 7-methyl isomer. Also, the 4-eth-oxy-phenyl groups are equatorially oriented on the bicycle as in its isomer. In the title compound, the cyclo-hexanone ring deviates from an ideal chair (total puckering amplitude Q(T) = 0.5390 Å) and the piperidone ring is closer to an ideal chair (Q(T) = 0.6064 Å). These Q(T) values are very similar to those of its isomer. Even though a center of symmetry passes through the 7-methyl analog, the benzene rings are oriented 26.11 (3)° with respect to each other, whereas the orientation is 53.10 (3)° for the title compound. The title compound exhibits inter-molecular N-H⋯O inter-actions [H⋯A = 2.25 (2) Å, versus 2.26 (2) Å for the analog].

Related literature

For the synthesis, stereochemistry and biological activities of 3-aza­bicyclo­[3.3.1]nonan-9-ones, see: Park et al. (2011a ▶, 2012a ▶). For analogous structures, see: Park et al. (2012b ▶, 2012c ▶); Parthiban et al. (2011b ▶, 2011c ▶). For ring puckering parameters, see: Cremer & Pople (1975 ▶).

Experimental

Crystal data

C25H30NO3

M = 392.50

Orthorhombic,

a = 11.9280 (4) Å

b = 26.1702 (14) Å

c = 6.9656 (3) Å

V = 2174.37 (17) Å3

Z = 4

Mo Kα radiation

μ = 0.08 mm−1

T = 298 K

0.35 × 0.28 × 0.15 mm

Data collection

Bruker APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2004 ▶) T min = 0.973, T max = 0.988

7809 measured reflections

2396 independent reflections

1689 reflections with I > 2σ(I)

R int = 0.029

Refinement

R[F 2 > 2σ(F 2)] = 0.047

wR(F 2) = 0.133

S = 1.06

2396 reflections

147 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.22 e Å−3

Δρmin = −0.17 e Å−3

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: APEX2 and SAINT-Plus (Bruker, 2004 ▶); data reduction: SAINT-Plus and XPREP (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 datablock(s) global, I. DOI: 10.1107/S1600536812039840/bq2375sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812039840/bq2375Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536812039840/bq2375Isup3.cml

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

C25H30NO3	F(000) = 844
Mr = 392.50	Dx = 1.199 Mg m−3
Orthorhombic, Pnma	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2n	Cell parameters from 3421 reflections
a = 11.9280 (4) Å	θ = 3.0–27.7°
b = 26.1702 (14) Å	µ = 0.08 mm−1
c = 6.9656 (3) Å	T = 298 K
V = 2174.37 (17) Å3	Block, colourless
Z = 4	0.35 × 0.28 × 0.15 mm

Bruker APEXII CCD area-detector diffractometer	2396 independent reflections
Radiation source: fine-focus sealed tube	1689 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.029
phi and ω scans	θmax = 28.4°, θmin = 3.0°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −15→14
Tmin = 0.973, Tmax = 0.988	k = −33→25
7809 measured reflections	l = −8→8

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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.133	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ2(Fo2) + (0.0613P)2 + 0.3421P] where P = (Fo2 + 2Fc2)/3
2396 reflections	(Δ/σ)max < 0.001
147 parameters	Δρmax = 0.22 e Å−3
0 restraints	Δρmin = −0.17 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 takeninto account individually in the estimation of e.s.d.'s in distances, anglesand torsion angles; correlations between e.s.d.'s in cell parameters are onlyused 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	Occ. (<1)
C1	0.55634 (11)	0.70312 (5)	0.13583 (19)	0.0350 (4)
H1	0.5180	0.7037	0.2603	0.042*
C2	0.46403 (11)	0.70192 (6)	−0.0240 (2)	0.0419 (4)
C3	0.39793 (16)	0.7500	0.0051 (3)	0.0444 (6)
C4	0.57166 (18)	0.7500	−0.2899 (3)	0.0487 (6)
H4A	0.5826	0.7500	−0.4279	0.058*
H4B	0.6450	0.7500	−0.2296	0.058*
C5	0.50932 (12)	0.70215 (7)	−0.2323 (2)	0.0511 (5)
H5A	0.5591	0.6731	−0.2482	0.061*
H5B	0.4467	0.6975	−0.3195	0.061*
C6	0.63304 (11)	0.65729 (5)	0.1344 (2)	0.0360 (4)
C7	0.72669 (13)	0.65458 (6)	0.0151 (2)	0.0445 (4)
H7	0.7415	0.6814	−0.0687	0.053*
C8	0.79747 (13)	0.61325 (6)	0.0183 (2)	0.0464 (4)
H8	0.8589	0.6123	−0.0638	0.056*
C9	0.77820 (12)	0.57292 (6)	0.1430 (2)	0.0415 (4)
C10	0.68483 (13)	0.57420 (6)	0.2607 (2)	0.0468 (4)
H10	0.6697	0.5471	0.3433	0.056*
C11	0.61410 (12)	0.61616 (6)	0.2545 (2)	0.0440 (4)
H11	0.5515	0.6167	0.3341	0.053*
C12	0.84722 (15)	0.49538 (6)	0.2799 (2)	0.0564 (5)
H12A	0.7787	0.4760	0.2626	0.068*
H12B	0.8457	0.5107	0.4066	0.068*
C13	0.94628 (17)	0.46091 (7)	0.2622 (3)	0.0651 (5)
H13A	0.9492	0.4471	0.1347	0.098*
H13B	0.9398	0.4335	0.3533	0.098*
H13C	1.0135	0.4799	0.2873	0.098*
C14	0.3844 (2)	0.66095 (12)	−0.0007 (4)	0.0431 (7)	0.50
H14A	0.3580	0.6604	0.1295	0.065*	0.50
H14B	0.4199	0.6290	−0.0301	0.065*	0.50
H14C	0.3222	0.6662	−0.0860	0.065*	0.50
N1	0.62172 (13)	0.7500	0.1205 (2)	0.0327 (4)
O1	0.29964 (12)	0.7500	0.0541 (3)	0.0738 (6)
O2	0.85487 (9)	0.53399 (4)	0.13792 (16)	0.0533 (3)
H1N	0.6708 (19)	0.7500	0.211 (3)	0.039 (6)*

	U11	U22	U33	U12	U13	U23
C1	0.0331 (6)	0.0380 (9)	0.0340 (8)	−0.0042 (7)	0.0035 (5)	0.0000 (6)
C2	0.0309 (7)	0.0523 (11)	0.0425 (8)	−0.0109 (7)	−0.0005 (6)	−0.0055 (7)
C3	0.0272 (9)	0.0715 (17)	0.0343 (11)	0.000	−0.0034 (7)	0.000
C4	0.0385 (10)	0.0767 (17)	0.0310 (11)	0.000	0.0012 (8)	0.000
C5	0.0407 (7)	0.0714 (12)	0.0411 (9)	−0.0051 (9)	−0.0045 (6)	−0.0121 (8)
C6	0.0358 (7)	0.0327 (9)	0.0394 (8)	−0.0046 (6)	0.0022 (6)	0.0006 (6)
C7	0.0460 (8)	0.0342 (9)	0.0534 (9)	−0.0021 (7)	0.0130 (7)	0.0109 (7)
C8	0.0432 (8)	0.0413 (10)	0.0545 (9)	0.0028 (8)	0.0149 (7)	0.0096 (7)
C9	0.0458 (8)	0.0326 (8)	0.0462 (9)	0.0019 (7)	0.0037 (6)	0.0032 (7)
C10	0.0517 (9)	0.0389 (9)	0.0498 (9)	−0.0017 (8)	0.0087 (7)	0.0134 (7)
C11	0.0420 (8)	0.0440 (10)	0.0459 (9)	−0.0016 (7)	0.0109 (6)	0.0079 (7)
C12	0.0664 (11)	0.0465 (11)	0.0563 (10)	0.0091 (9)	0.0037 (8)	0.0147 (8)
C13	0.0728 (12)	0.0554 (12)	0.0672 (12)	0.0188 (10)	−0.0016 (9)	0.0133 (9)
C14	0.0435 (15)	0.0369 (18)	0.0488 (17)	−0.0060 (14)	0.0005 (13)	−0.0014 (14)
N1	0.0284 (8)	0.0319 (10)	0.0379 (9)	0.000	−0.0063 (7)	0.000
O1	0.0278 (7)	0.1163 (17)	0.0774 (12)	0.000	0.0094 (7)	0.000
O2	0.0591 (7)	0.0415 (7)	0.0594 (7)	0.0129 (6)	0.0127 (5)	0.0146 (5)

C1—N1	1.4577 (16)	C8—C9	1.386 (2)
C1—C6	1.5084 (19)	C8—H8	0.9300
C1—C2	1.5661 (19)	C9—O2	1.3696 (18)
C1—H1	0.9800	C9—C10	1.383 (2)
C2—C14	1.442 (3)	C10—C11	1.385 (2)
C2—C3	1.4986 (19)	C10—H10	0.9300
C2—C5	1.549 (2)	C11—H11	0.9300
C3—O1	1.221 (2)	C12—O2	1.4169 (18)
C3—C2i	1.4986 (19)	C12—C13	1.492 (2)
C4—C5	1.511 (2)	C12—H12A	0.9700
C4—C5i	1.511 (2)	C12—H12B	0.9700
C4—H4A	0.9700	C13—H13A	0.9600
C4—H4B	0.9700	C13—H13B	0.9600
C5—H5A	0.9700	C13—H13C	0.9600
C5—H5B	0.9700	C14—H14A	0.9600
C6—C11	1.3817 (19)	C14—H14B	0.9600
C6—C7	1.394 (2)	C14—H14C	0.9600
C7—C8	1.372 (2)	N1—C1i	1.4577 (16)
C7—H7	0.9300	N1—H1N	0.86 (2)
N1—C1—C6	110.13 (11)	C7—C8—H8	119.7
N1—C1—C2	109.94 (12)	C9—C8—H8	119.7
C6—C1—C2	113.94 (11)	O2—C9—C10	124.82 (13)
N1—C1—H1	107.5	O2—C9—C8	116.07 (12)
C6—C1—H1	107.5	C10—C9—C8	119.11 (14)
C2—C1—H1	107.5	C9—C10—C11	119.40 (14)
C14—C2—C3	105.22 (16)	C9—C10—H10	120.3
C14—C2—C5	109.76 (16)	C11—C10—H10	120.3
C3—C2—C5	107.89 (14)	C6—C11—C10	122.48 (13)
C14—C2—C1	113.46 (17)	C6—C11—H11	118.8
C3—C2—C1	104.89 (12)	C10—C11—H11	118.8
C5—C2—C1	114.89 (11)	O2—C12—C13	108.82 (14)
O1—C3—C2	122.89 (8)	O2—C12—H12A	109.9
O1—C3—C2i	122.89 (8)	C13—C12—H12A	109.9
C2—C3—C2i	114.19 (16)	O2—C12—H12B	109.9
C5—C4—C5i	112.00 (17)	C13—C12—H12B	109.9
C5—C4—H4A	109.2	H12A—C12—H12B	108.3
C5i—C4—H4A	109.2	C12—C13—H13A	109.5
C5—C4—H4B	109.2	C12—C13—H13B	109.5
C5i—C4—H4B	109.2	H13A—C13—H13B	109.5
H4A—C4—H4B	107.9	C12—C13—H13C	109.5
C4—C5—C2	115.05 (14)	H13A—C13—H13C	109.5
C4—C5—H5A	108.5	H13B—C13—H13C	109.5
C2—C5—H5A	108.5	C2—C14—H14A	109.5
C4—C5—H5B	108.5	C2—C14—H14B	109.5
C2—C5—H5B	108.5	H14A—C14—H14B	109.5
H5A—C5—H5B	107.5	C2—C14—H14C	109.5
C11—C6—C7	116.88 (13)	H14A—C14—H14C	109.5
C11—C6—C1	121.07 (12)	H14B—C14—H14C	109.5
C7—C6—C1	122.04 (12)	C1—N1—C1i	114.64 (14)
C8—C7—C6	121.55 (14)	C1—N1—H1N	108.1 (7)
C8—C7—H7	119.2	C1i—N1—H1N	108.1 (7)
C6—C7—H7	119.2	C9—O2—C12	117.99 (12)
C7—C8—C9	120.56 (13)
N1—C1—C2—C14	−170.69 (17)	N1—C1—C6—C7	−39.74 (18)
C6—C1—C2—C14	65.14 (19)	C2—C1—C6—C7	84.32 (17)
N1—C1—C2—C3	−56.39 (15)	C11—C6—C7—C8	−0.7 (2)
C6—C1—C2—C3	179.44 (11)	C1—C6—C7—C8	178.36 (14)
N1—C1—C2—C5	61.89 (17)	C6—C7—C8—C9	−0.7 (2)
C6—C1—C2—C5	−62.28 (17)	C7—C8—C9—O2	−178.74 (14)
C14—C2—C3—O1	5.4 (3)	C7—C8—C9—C10	1.8 (2)
C5—C2—C3—O1	122.6 (2)	O2—C9—C10—C11	179.14 (14)
C1—C2—C3—O1	−114.5 (2)	C8—C9—C10—C11	−1.4 (2)
C14—C2—C3—C2i	−176.73 (16)	C7—C6—C11—C10	1.1 (2)
C5—C2—C3—C2i	−59.60 (19)	C1—C6—C11—C10	−178.02 (14)
C1—C2—C3—C2i	63.32 (19)	C9—C10—C11—C6	0.0 (2)
C5i—C4—C5—C2	−46.7 (2)	C6—C1—N1—C1i	−175.39 (10)
C14—C2—C5—C4	166.11 (18)	C2—C1—N1—C1i	58.26 (18)
C3—C2—C5—C4	51.97 (17)	C10—C9—O2—C12	−8.8 (2)
C1—C2—C5—C4	−64.62 (19)	C8—C9—O2—C12	171.71 (15)
N1—C1—C6—C11	139.30 (14)	C13—C12—O2—C9	−173.00 (14)
C2—C1—C6—C11	−96.64 (16)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O1ii	0.86 (2)	2.25 (2)	3.105 (2)	180 (2)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯O1i	0.86 (2)	2.25 (2)	3.105 (2)	180 (2)

Symmetry code: (i) .