2,4-Bis(4-eth-oxy-phen-yl)-7-methyl-3-aza-bicyclo-[3.3.1]nonan-9-one.

The mol-ecule of the title compound, C(25)H(31)NO(3), exists in a twin-chair conformation with an equatorial orientation of the 4-eth-oxy-phenyl groups, as observed for its ortho isomer [Parthiban, Ramkumar, Park & Jeong (2011b ▶), Acta Cryst. E67, o1475-o1476]. The methyl and 4-eth-oxy-phenyl groups are also equatorially oriented on the bicycle, as in the ortho analogue. In particular, although the cyclo-hexa-none ring deviates from an ideal chair, the piperidone ring is closer to an ideal chair, whereas in the ortho isomer both rings are significantly puckered and deviate from ideal chairs. The 4-eth-oxy-phenyl groups on both sides of the secondary amine group are oriented at an angle of 26.11 (3)° with respect to each other, but the 2-eth-oxy-phenyl groups in the ortho isomer are oriented by less than half this [12.41 (4)°]. In contrast to the absence of any significant inter-actions in the crystal packing of the ortho isomer, the title compound features N-H⋯O inter-actions, linking the mol-ecules along the b axis.

Related literature

For the synthesis and stereochemistry of 3-aza­bicyclo­[3.3.1] nonan-9-ones, see: Park et al. (2011 ▶). For the biological activities of 3-aza­bicyclo­[3.3.1]nonan-9-ones, see: Barker et al. (2005 ▶); Parthiban et al. (2009 ▶, 2010a ▶,b ▶,2011a ▶). For a related structure, see: Parthiban et al. (2011b ▶). For ring-puckering parameters, see: Cremer & Pople (1975 ▶); Nardelli (1983 ▶).

Experimental

Crystal data

C25H31NO3

M = 393.51

Orthorhombic,

a = 19.329 (4) Å

b = 6.7967 (12) Å

c = 8.2501 (16) Å

V = 1083.8 (4) Å3

Z = 2

Mo Kα radiation

μ = 0.08 mm−1

T = 298 K

0.35 × 0.28 × 0.10 mm

Data collection

Bruker APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2004 ▶) T min = 0.973, T max = 0.992

1565 measured reflections

1165 independent reflections

950 reflections with I > 2σ(I)

R int = 0.015

Refinement

R[F 2 > 2σ(F 2)] = 0.037

wR(F 2) = 0.094

S = 1.05

1165 reflections

150 parameters

4 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.12 e Å−3

Δρmin = −0.16 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/S1600536812006563/bq2338sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812006563/bq2338Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536812006563/bq2338Isup3.cml

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

C25H31NO3	F(000) = 424
Mr = 393.51	Dx = 1.206 Mg m−3
Orthorhombic, Pmn21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac -2	Cell parameters from 1281 reflections
a = 19.329 (4) Å	θ = 2.5–22.3°
b = 6.7967 (12) Å	µ = 0.08 mm−1
c = 8.2501 (16) Å	T = 298 K
V = 1083.8 (4) Å3	Block, colourless
Z = 2	0.35 × 0.28 × 0.10 mm

Bruker APEXII CCD area-detector diffractometer	1165 independent reflections
Radiation source: fine-focus sealed tube	950 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.015
φ and ω scans	θmax = 26.0°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = 0→23
Tmin = 0.973, Tmax = 0.992	k = 0→8
1565 measured reflections	l = −7→10

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)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.094	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ2(Fo2) + (0.0502P)2 + 0.0596P] where P = (Fo2 + 2Fc2)/3
1165 reflections	(Δ/σ)max < 0.001
150 parameters	Δρmax = 0.12 e Å−3
4 restraints	Δρmin = −0.16 e Å−3

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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	0.06340 (12)	0.4381 (3)	0.8529 (3)	0.0363 (6)
H1	0.0632	0.4085	0.7366	0.044*
C2	0.06391 (13)	0.2389 (3)	0.9456 (3)	0.0389 (6)
H2	0.1044	0.1628	0.9112	0.047*
C3	0.0000	0.1332 (5)	0.8932 (5)	0.0415 (8)
C4	0.06491 (14)	0.2575 (4)	1.1304 (3)	0.0477 (7)
H4A	0.0714	0.1276	1.1767	0.057*
H4B	0.1044	0.3370	1.1615	0.057*
C5	0.0000	0.3480 (6)	1.2034 (4)	0.0489 (10)
H5	0.0000	0.4887	1.1772	0.059*
C6	0.0000	0.3276 (10)	1.3882 (6)	0.0786 (15)
C7	0.12754 (11)	0.5559 (3)	0.8882 (3)	0.0349 (6)
C8	0.12963 (12)	0.7124 (4)	0.9938 (3)	0.0397 (6)
H8	0.0895	0.7477	1.0489	0.048*
C9	0.18980 (12)	0.8191 (4)	1.0205 (3)	0.0434 (6)
H9	0.1898	0.9248	1.0921	0.052*
C10	0.24949 (12)	0.7671 (4)	0.9402 (3)	0.0415 (6)
C11	0.24911 (14)	0.6067 (4)	0.8392 (4)	0.0517 (8)
H11	0.2898	0.5676	0.7885	0.062*
C12	0.18887 (13)	0.5027 (4)	0.8122 (4)	0.0463 (6)
H12	0.1893	0.3956	0.7421	0.056*
C13	0.31170 (14)	1.0533 (4)	1.0305 (4)	0.0610 (8)
H13A	0.3057	1.0357	1.1463	0.073*
H13B	0.2741	1.1343	0.9905	0.073*
C14	0.37939 (15)	1.1511 (5)	0.9972 (5)	0.0731 (10)
H14A	0.4162	1.0730	1.0414	0.110*
H14B	0.3798	1.2790	1.0466	0.110*
H14C	0.3856	1.1643	0.8823	0.110*
N1	0.0000	0.5455 (4)	0.8897 (4)	0.0361 (7)
O1	0.0000	−0.0133 (4)	0.8084 (4)	0.0603 (8)
O2	0.31106 (9)	0.8665 (3)	0.9511 (3)	0.0599 (6)
H1A	0.0000	0.656 (3)	0.840 (4)	0.033 (10)*
H6A	−0.0436 (13)	0.385 (5)	1.427 (5)	0.091 (12)*
H6B	0.0000	0.189 (4)	1.421 (7)	0.089 (18)*

	U11	U22	U33	U12	U13	U23
C1	0.0373 (14)	0.0399 (13)	0.0318 (12)	0.0017 (10)	0.0031 (10)	0.0015 (11)
C2	0.0344 (13)	0.0350 (12)	0.0471 (13)	0.0070 (10)	0.0024 (12)	0.0050 (13)
C3	0.050 (2)	0.0315 (18)	0.0426 (18)	0.000	0.000	0.0048 (19)
C4	0.0452 (17)	0.0520 (15)	0.0459 (14)	−0.0029 (12)	−0.0086 (12)	0.0147 (14)
C5	0.057 (3)	0.053 (2)	0.0369 (18)	0.000	0.000	0.005 (2)
C6	0.095 (4)	0.103 (4)	0.038 (2)	0.000	0.000	0.008 (3)
C7	0.0319 (13)	0.0376 (13)	0.0353 (12)	0.0030 (10)	0.0060 (10)	0.0055 (12)
C8	0.0310 (12)	0.0453 (13)	0.0428 (13)	0.0050 (10)	0.0055 (10)	−0.0038 (13)
C9	0.0406 (14)	0.0435 (13)	0.0461 (13)	0.0031 (11)	0.0023 (12)	−0.0054 (14)
C10	0.0334 (13)	0.0414 (13)	0.0498 (13)	−0.0003 (11)	0.0052 (12)	−0.0004 (13)
C11	0.0369 (15)	0.0466 (15)	0.0717 (19)	0.0010 (12)	0.0197 (14)	−0.0083 (16)
C12	0.0442 (16)	0.0390 (13)	0.0556 (14)	0.0017 (12)	0.0131 (12)	−0.0078 (14)
C13	0.0543 (18)	0.0615 (18)	0.0672 (19)	−0.0074 (13)	0.0053 (15)	−0.0171 (18)
C14	0.065 (2)	0.076 (2)	0.079 (2)	−0.0226 (17)	0.0056 (18)	−0.021 (2)
N1	0.0317 (16)	0.0324 (16)	0.0441 (16)	0.000	0.000	0.0075 (14)
O1	0.073 (2)	0.0366 (14)	0.0713 (18)	0.000	0.000	−0.0071 (16)
O2	0.0388 (10)	0.0547 (11)	0.0862 (14)	−0.0084 (9)	0.0101 (10)	−0.0158 (13)

C1—N1	1.458 (3)	C8—C9	1.388 (3)
C1—C7	1.504 (3)	C8—H8	0.9300
C1—C2	1.555 (3)	C9—C10	1.376 (3)
C1—H1	0.9800	C9—H9	0.9300
C2—C3	1.493 (3)	C10—O2	1.371 (3)
C2—C4	1.530 (4)	C10—C11	1.373 (4)
C2—H2	0.9800	C11—C12	1.380 (3)
C3—O1	1.216 (4)	C11—H11	0.9300
C3—C2i	1.493 (3)	C12—H12	0.9300
C4—C5	1.521 (4)	C13—O2	1.429 (3)
C4—H4A	0.9700	C13—C14	1.493 (4)
C4—H4B	0.9700	C13—H13A	0.9700
C5—C4i	1.521 (4)	C13—H13B	0.9700
C5—C6	1.531 (6)	C14—H14A	0.9600
C5—H5	0.9800	C14—H14B	0.9600
C6—H6A	0.980 (18)	C14—H14C	0.9600
C6—H6B	0.98 (2)	N1—C1i	1.458 (3)
C7—C8	1.375 (3)	N1—H1A	0.855 (18)
C7—C12	1.389 (3)
N1—C1—C7	112.68 (19)	C12—C7—C1	118.5 (2)
N1—C1—C2	109.8 (2)	C7—C8—C9	122.0 (2)
C7—C1—C2	111.28 (19)	C7—C8—H8	119.0
N1—C1—H1	107.6	C9—C8—H8	119.0
C7—C1—H1	107.6	C10—C9—C8	119.4 (2)
C2—C1—H1	107.6	C10—C9—H9	120.3
C3—C2—C4	109.8 (2)	C8—C9—H9	120.3
C3—C2—C1	105.8 (2)	O2—C10—C11	115.8 (2)
C4—C2—C1	114.7 (2)	O2—C10—C9	124.7 (2)
C3—C2—H2	108.8	C11—C10—C9	119.5 (2)
C4—C2—H2	108.8	C10—C11—C12	120.6 (2)
C1—C2—H2	108.8	C10—C11—H11	119.7
O1—C3—C2	124.08 (16)	C12—C11—H11	119.7
O1—C3—C2i	124.08 (16)	C11—C12—C7	120.9 (3)
C2—C3—C2i	111.6 (3)	C11—C12—H12	119.5
C5—C4—C2	114.6 (2)	C7—C12—H12	119.5
C5—C4—H4A	108.6	O2—C13—C14	108.6 (2)
C2—C4—H4A	108.6	O2—C13—H13A	110.0
C5—C4—H4B	108.6	C14—C13—H13A	110.0
C2—C4—H4B	108.6	O2—C13—H13B	110.0
H4A—C4—H4B	107.6	C14—C13—H13B	110.0
C4i—C5—C4	111.1 (3)	H13A—C13—H13B	108.3
C4i—C5—C6	110.9 (2)	C13—C14—H14A	109.5
C4—C5—C6	110.9 (2)	C13—C14—H14B	109.5
C4i—C5—H5	107.9	H14A—C14—H14B	109.5
C4—C5—H5	107.9	C13—C14—H14C	109.5
C6—C5—H5	107.9	H14A—C14—H14C	109.5
C5—C6—H6A	107 (3)	H14B—C14—H14C	109.5
C5—C6—H6B	111 (4)	C1i—N1—C1	114.3 (3)
H6A—C6—H6B	107 (3)	C1i—N1—H1A	109.9 (10)
C8—C7—C12	117.5 (2)	C1—N1—H1A	109.9 (10)
C8—C7—C1	124.0 (2)	C10—O2—C13	118.37 (19)
N1—C1—C2—C3	57.5 (3)	C12—C7—C8—C9	2.2 (4)
C7—C1—C2—C3	−177.0 (2)	C1—C7—C8—C9	−178.9 (2)
N1—C1—C2—C4	−63.6 (3)	C7—C8—C9—C10	−0.4 (4)
C7—C1—C2—C4	61.9 (3)	C8—C9—C10—O2	176.9 (2)
C4—C2—C3—O1	−125.3 (4)	C8—C9—C10—C11	−2.1 (4)
C1—C2—C3—O1	110.4 (4)	O2—C10—C11—C12	−176.3 (3)
C4—C2—C3—C2i	59.6 (4)	C9—C10—C11—C12	2.8 (4)
C1—C2—C3—C2i	−64.7 (3)	C10—C11—C12—C7	−1.0 (4)
C3—C2—C4—C5	−53.1 (3)	C8—C7—C12—C11	−1.5 (4)
C1—C2—C4—C5	65.9 (3)	C1—C7—C12—C11	179.5 (2)
C2—C4—C5—C4i	46.1 (4)	C7—C1—N1—C1i	178.43 (16)
C2—C4—C5—C6	170.0 (3)	C2—C1—N1—C1i	−56.9 (3)
N1—C1—C7—C8	22.0 (3)	C11—C10—O2—C13	169.0 (3)
C2—C1—C7—C8	−101.9 (3)	C9—C10—O2—C13	−10.0 (4)
N1—C1—C7—C12	−159.1 (2)	C14—C13—O2—C10	−168.2 (3)
C2—C1—C7—C12	77.1 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1ii	0.86 (2)	2.26 (2)	3.073 (4)	158 (3)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O1i	0.86 (2)	2.26 (2)	3.073 (4)	158 (3)

Symmetry code: (i) .