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

The crystal structure of the title compound, C(25)H(31)NO(3), exists in a twin-chair conformation with an equatorial orientation of the ortho-eth-oxy-phenyl groups. According to Cremer and Pople [Cremer & Pople (1975 ▶), J. Am. Chem. Soc. 97, 1354-1358], both the piperidone and cyclo-hexa-none rings are significantly puckered with total puckering amplitutdes Q(T) of 0.5889 (18) and 0.554 (2) Å, respectively. The ortho-eth-oxy-phenyl groups are located on either side of the secondary amino group and make a dihedral angle of 12.41 (4)° with respect to each other. The methyl group on the cyclo-hexa-none part occupies an exocyclic equatorial disposition. The crystal packing is stabilized by weak van der Waals inter-actions.

Related literature

For the synthesis and biological activity of 3-aza­bicyclo­[3.3.1]nonan-9-ones, see: Jeyaraman & Avila (1981 ▶); Barker et al. (2005 ▶); Parthiban et al. (2009a ▶, 2010b ▶,c ▶, 2011 ▶). For related structures, see: Parthiban et al. (2009b ▶,c ▶, 2010a ▶,c ▶); Cox et al. (1985 ▶); Smith-Verdier et al. (1983 ▶); Padegimas & Kovacic (1972 ▶). For ring puckering parameters, see: Cremer & Pople (1975 ▶); Nardelli (1983 ▶).

Experimental

Crystal data

C25H31NO3

M = 393.51

Monoclinic,

a = 10.3147 (6) Å

b = 11.8817 (6) Å

c = 18.7809 (10) Å

β = 100.866 (2)°

V = 2260.4 (2) 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 = 0.974, T max = 0.989

12446 measured reflections

3876 independent reflections

2415 reflections with I > 2σ(I)

R int = 0.025

Refinement

R[F 2 > 2σ(F 2)] = 0.042

wR(F 2) = 0.117

S = 1.03

3876 reflections

269 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.12 e Å−3

Δρmin = −0.13 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 datablocks global, I. DOI: 10.1107/S1600536811018472/lw2064sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811018472/lw2064Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536811018472/lw2064Isup3.cml

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

C25H31NO3	F(000) = 848
Mr = 393.51	Dx = 1.156 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 3407 reflections
a = 10.3147 (6) Å	θ = 2.6–21.8°
b = 11.8817 (6) Å	µ = 0.08 mm−1
c = 18.7809 (10) Å	T = 298 K
β = 100.866 (2)°	Block, colourless
V = 2260.4 (2) Å3	0.35 × 0.28 × 0.15 mm
Z = 4

Bruker APEXII CCD area-detector diffractometer	3876 independent reflections
Radiation source: fine-focus sealed tube	2415 reflections with I > 2σ(I)
graphite	Rint = 0.025
φ and ω scans	θmax = 25.6°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −10→11
Tmin = 0.974, Tmax = 0.989	k = −14→14
12446 measured reflections	l = −22→16

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)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.117	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ2(Fo2) + (0.047P)2 + 0.3732P] where P = (Fo2 + 2Fc2)/3
3876 reflections	(Δ/σ)max < 0.001
269 parameters	Δρmax = 0.12 e Å−3
0 restraints	Δρmin = −0.13 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
C1	1.07118 (17)	0.68920 (14)	0.12439 (9)	0.0475 (4)
H1	1.1292	0.6243	0.1379	0.057*
C2	0.99532 (18)	0.71301 (15)	0.18699 (9)	0.0553 (5)
H2	1.0598	0.7203	0.2323	0.066*
C3	0.9088 (2)	0.81806 (16)	0.17738 (11)	0.0676 (6)
H3A	0.8763	0.8312	0.2219	0.081*
H3B	0.9629	0.8821	0.1698	0.081*
C4	0.7921 (2)	0.81182 (16)	0.11504 (11)	0.0659 (6)
H4	0.8258	0.8178	0.0698	0.079*
C5	0.72060 (18)	0.70069 (16)	0.11430 (10)	0.0585 (5)
H5A	0.6605	0.6933	0.0681	0.070*
H5B	0.6678	0.7023	0.1519	0.070*
C6	0.80887 (17)	0.59660 (14)	0.12573 (8)	0.0489 (4)
H6	0.7547	0.5311	0.1324	0.059*
C7	0.88565 (16)	0.57076 (14)	0.06386 (8)	0.0454 (4)
H7	0.9362	0.5012	0.0759	0.054*
C8	0.90968 (17)	0.61391 (15)	0.19325 (9)	0.0522 (5)
C9	1.15495 (18)	0.78883 (15)	0.11170 (10)	0.0522 (5)
C10	1.1188 (2)	0.86086 (16)	0.05364 (11)	0.0643 (5)
H10	1.0419	0.8464	0.0202	0.077*
C11	1.1939 (3)	0.95391 (18)	0.04389 (15)	0.0868 (7)
H11	1.1680	1.0011	0.0042	0.104*
C12	1.3066 (3)	0.9759 (2)	0.09300 (18)	0.0975 (8)
H12	1.3576	1.0384	0.0866	0.117*
C13	1.3453 (2)	0.9065 (2)	0.15186 (15)	0.0861 (7)
H13	1.4219	0.9224	0.1852	0.103*
C14	1.27035 (19)	0.81263 (17)	0.16149 (11)	0.0629 (5)
C15	0.79067 (17)	0.55378 (15)	−0.00749 (9)	0.0495 (5)
C16	0.71335 (18)	0.45680 (16)	−0.01864 (10)	0.0569 (5)
C17	0.6211 (2)	0.4422 (2)	−0.08214 (12)	0.0741 (6)
H17	0.5700	0.3773	−0.0892	0.089*
C18	0.6060 (2)	0.5244 (3)	−0.13440 (12)	0.0885 (8)
H18	0.5439	0.5150	−0.1768	0.106*
C19	0.6809 (2)	0.6193 (2)	−0.12479 (11)	0.0871 (7)
H19	0.6707	0.6743	−0.1607	0.105*
C20	0.7721 (2)	0.63362 (18)	−0.06142 (10)	0.0671 (6)
H20	0.8223	0.6991	−0.0551	0.080*
C21	0.6966 (3)	0.9105 (2)	0.11769 (15)	0.1095 (9)
H21A	0.6663	0.9092	0.1630	0.164*
H21B	0.6225	0.9037	0.0785	0.164*
H21C	0.7414	0.9803	0.1133	0.164*
C22	1.4219 (2)	0.7531 (3)	0.26893 (13)	0.1002 (9)
H22A	1.4220	0.8246	0.2938	0.120*
H22B	1.4965	0.7517	0.2442	0.120*
C23	1.4315 (3)	0.6584 (3)	0.32186 (15)	0.1209 (11)
H23A	1.3550	0.6583	0.3441	0.181*
H23B	1.5093	0.6676	0.3585	0.181*
H23C	1.4365	0.5883	0.2970	0.181*
C24	0.6380 (2)	0.29441 (18)	0.03834 (13)	0.0819 (7)
H24A	0.6386	0.2398	0.0000	0.098*
H24B	0.5510	0.3284	0.0315	0.098*
C25	0.6690 (3)	0.2388 (2)	0.10965 (16)	0.1147 (10)
H25A	0.7545	0.2041	0.1155	0.172*
H25B	0.6037	0.1823	0.1127	0.172*
H25C	0.6691	0.2936	0.1472	0.172*
H1N	1.0230 (17)	0.6437 (14)	0.0263 (9)	0.054 (6)*
N1	0.97762 (14)	0.66179 (12)	0.05778 (8)	0.0461 (4)
O1	0.92001 (15)	0.55398 (12)	0.24612 (7)	0.0837 (5)
O2	1.30161 (13)	0.73934 (13)	0.21804 (7)	0.0743 (4)
O3	0.73609 (13)	0.37931 (11)	0.03597 (7)	0.0719 (4)

	U11	U22	U33	U12	U13	U23
C1	0.0384 (11)	0.0552 (10)	0.0466 (10)	−0.0026 (8)	0.0018 (8)	−0.0035 (8)
C2	0.0484 (12)	0.0740 (12)	0.0406 (9)	−0.0126 (10)	0.0011 (8)	−0.0080 (9)
C3	0.0705 (15)	0.0652 (13)	0.0748 (13)	−0.0188 (11)	0.0337 (12)	−0.0210 (10)
C4	0.0688 (14)	0.0615 (12)	0.0749 (13)	0.0125 (11)	0.0328 (12)	0.0059 (10)
C5	0.0434 (12)	0.0802 (13)	0.0527 (11)	0.0004 (10)	0.0108 (9)	−0.0027 (9)
C6	0.0473 (11)	0.0536 (10)	0.0453 (10)	−0.0099 (9)	0.0079 (8)	0.0020 (8)
C7	0.0407 (11)	0.0469 (9)	0.0463 (9)	−0.0020 (8)	0.0023 (8)	−0.0020 (7)
C8	0.0509 (12)	0.0644 (11)	0.0411 (10)	0.0019 (9)	0.0079 (8)	0.0055 (9)
C9	0.0403 (11)	0.0596 (11)	0.0575 (11)	−0.0062 (9)	0.0114 (9)	−0.0097 (9)
C10	0.0566 (13)	0.0667 (12)	0.0722 (13)	−0.0074 (11)	0.0190 (10)	0.0011 (10)
C11	0.0885 (19)	0.0707 (15)	0.1100 (19)	−0.0106 (14)	0.0411 (16)	0.0105 (13)
C12	0.085 (2)	0.0778 (17)	0.141 (2)	−0.0335 (15)	0.0503 (18)	−0.0152 (17)
C13	0.0608 (15)	0.0964 (18)	0.1040 (19)	−0.0290 (14)	0.0232 (13)	−0.0319 (15)
C14	0.0456 (13)	0.0740 (13)	0.0710 (13)	−0.0138 (11)	0.0159 (11)	−0.0201 (11)
C15	0.0416 (11)	0.0620 (11)	0.0441 (10)	−0.0024 (9)	0.0057 (8)	−0.0078 (9)
C16	0.0497 (12)	0.0677 (12)	0.0534 (11)	−0.0044 (10)	0.0100 (9)	−0.0124 (10)
C17	0.0576 (14)	0.0973 (16)	0.0650 (13)	−0.0179 (12)	0.0051 (11)	−0.0303 (13)
C18	0.0680 (17)	0.140 (2)	0.0504 (13)	−0.0093 (16)	−0.0059 (11)	−0.0146 (15)
C19	0.0799 (17)	0.123 (2)	0.0516 (12)	−0.0099 (16)	−0.0059 (12)	0.0122 (13)
C20	0.0629 (14)	0.0857 (14)	0.0490 (11)	−0.0103 (11)	0.0014 (10)	0.0052 (10)
C21	0.119 (2)	0.0863 (17)	0.140 (2)	0.0412 (16)	0.0676 (19)	0.0127 (16)
C22	0.0462 (15)	0.170 (3)	0.0793 (16)	−0.0167 (16)	−0.0019 (13)	−0.0290 (18)
C23	0.088 (2)	0.179 (3)	0.0807 (18)	0.021 (2)	−0.0231 (15)	−0.0037 (19)
C24	0.0777 (16)	0.0658 (13)	0.1047 (18)	−0.0212 (12)	0.0236 (14)	−0.0183 (13)
C25	0.122 (2)	0.0769 (17)	0.147 (3)	−0.0075 (16)	0.029 (2)	0.0255 (17)
N1	0.0390 (9)	0.0585 (9)	0.0413 (8)	−0.0041 (7)	0.0088 (7)	−0.0067 (7)
O1	0.0861 (11)	0.1035 (11)	0.0580 (8)	−0.0004 (9)	0.0049 (7)	0.0331 (8)
O2	0.0478 (9)	0.0991 (11)	0.0686 (9)	−0.0109 (8)	−0.0083 (7)	−0.0111 (8)
O3	0.0709 (10)	0.0583 (8)	0.0812 (9)	−0.0193 (7)	0.0010 (8)	−0.0064 (7)

C1—N1	1.465 (2)	C13—H13	0.9300
C1—C9	1.511 (2)	C14—O2	1.364 (2)
C1—C2	1.556 (2)	C15—C20	1.375 (2)
C1—H1	0.9800	C15—C16	1.395 (2)
C2—C8	1.490 (2)	C16—O3	1.365 (2)
C2—C3	1.525 (3)	C16—C17	1.389 (3)
C2—H2	0.9800	C17—C18	1.372 (3)
C3—C4	1.515 (3)	C17—H17	0.9300
C3—H3A	0.9700	C18—C19	1.360 (3)
C3—H3B	0.9700	C18—H18	0.9300
C4—C5	1.511 (3)	C19—C20	1.381 (3)
C4—C21	1.539 (3)	C19—H19	0.9300
C4—H4	0.9800	C20—H20	0.9300
C5—C6	1.527 (2)	C21—H21A	0.9600
C5—H5A	0.9700	C21—H21B	0.9600
C5—H5B	0.9700	C21—H21C	0.9600
C6—C8	1.495 (2)	C22—O2	1.426 (2)
C6—C7	1.555 (2)	C22—C23	1.493 (4)
C6—H6	0.9800	C22—H22A	0.9700
C7—N1	1.457 (2)	C22—H22B	0.9700
C7—C15	1.517 (2)	C23—H23A	0.9600
C7—H7	0.9800	C23—H23B	0.9600
C8—O1	1.2101 (19)	C23—H23C	0.9600
C9—C10	1.381 (3)	C24—O3	1.436 (2)
C9—C14	1.397 (3)	C24—C25	1.474 (3)
C10—C11	1.382 (3)	C24—H24A	0.9700
C10—H10	0.9300	C24—H24B	0.9700
C11—C12	1.366 (3)	C25—H25A	0.9600
C11—H11	0.9300	C25—H25B	0.9600
C12—C13	1.377 (3)	C25—H25C	0.9600
C12—H12	0.9300	N1—H1N	0.848 (18)
C13—C14	1.388 (3)
N1—C1—C9	110.10 (14)	C12—C13—H13	119.9
N1—C1—C2	109.96 (14)	C14—C13—H13	119.9
C9—C1—C2	111.15 (14)	O2—C14—C13	123.9 (2)
N1—C1—H1	108.5	O2—C14—C9	116.01 (17)
C9—C1—H1	108.5	C13—C14—C9	120.1 (2)
C2—C1—H1	108.5	C20—C15—C16	117.59 (16)
C8—C2—C3	108.30 (15)	C20—C15—C7	122.44 (16)
C8—C2—C1	107.82 (14)	C16—C15—C7	119.90 (15)
C3—C2—C1	115.19 (15)	O3—C16—C17	123.62 (18)
C8—C2—H2	108.5	O3—C16—C15	115.60 (15)
C3—C2—H2	108.5	C17—C16—C15	120.78 (19)
C1—C2—H2	108.5	C18—C17—C16	119.5 (2)
C4—C3—C2	114.42 (15)	C18—C17—H17	120.2
C4—C3—H3A	108.7	C16—C17—H17	120.2
C2—C3—H3A	108.7	C19—C18—C17	120.7 (2)
C4—C3—H3B	108.7	C19—C18—H18	119.7
C2—C3—H3B	108.7	C17—C18—H18	119.7
H3A—C3—H3B	107.6	C18—C19—C20	119.6 (2)
C5—C4—C3	111.43 (15)	C18—C19—H19	120.2
C5—C4—C21	110.60 (18)	C20—C19—H19	120.2
C3—C4—C21	110.98 (18)	C15—C20—C19	121.9 (2)
C5—C4—H4	107.9	C15—C20—H20	119.1
C3—C4—H4	107.9	C19—C20—H20	119.1
C21—C4—H4	107.9	C4—C21—H21A	109.5
C4—C5—C6	115.42 (15)	C4—C21—H21B	109.5
C4—C5—H5A	108.4	H21A—C21—H21B	109.5
C6—C5—H5A	108.4	C4—C21—H21C	109.5
C4—C5—H5B	108.4	H21A—C21—H21C	109.5
C6—C5—H5B	108.4	H21B—C21—H21C	109.5
H5A—C5—H5B	107.5	O2—C22—C23	107.5 (2)
C8—C6—C5	107.99 (14)	O2—C22—H22A	110.2
C8—C6—C7	106.87 (14)	C23—C22—H22A	110.2
C5—C6—C7	115.41 (14)	O2—C22—H22B	110.2
C8—C6—H6	108.8	C23—C22—H22B	110.2
C5—C6—H6	108.8	H22A—C22—H22B	108.5
C7—C6—H6	108.8	C22—C23—H23A	109.5
N1—C7—C15	110.55 (13)	C22—C23—H23B	109.5
N1—C7—C6	110.04 (13)	H23A—C23—H23B	109.5
C15—C7—C6	110.56 (13)	C22—C23—H23C	109.5
N1—C7—H7	108.5	H23A—C23—H23C	109.5
C15—C7—H7	108.5	H23B—C23—H23C	109.5
C6—C7—H7	108.5	O3—C24—C25	108.05 (19)
O1—C8—C2	124.61 (16)	O3—C24—H24A	110.1
O1—C8—C6	123.69 (17)	C25—C24—H24A	110.1
C2—C8—C6	111.70 (14)	O3—C24—H24B	110.1
C10—C9—C14	118.18 (18)	C25—C24—H24B	110.1
C10—C9—C1	122.21 (16)	H24A—C24—H24B	108.4
C14—C9—C1	119.57 (17)	C24—C25—H25A	109.5
C9—C10—C11	121.7 (2)	C24—C25—H25B	109.5
C9—C10—H10	119.1	H25A—C25—H25B	109.5
C11—C10—H10	119.1	C24—C25—H25C	109.5
C12—C11—C10	119.4 (2)	H25A—C25—H25C	109.5
C12—C11—H11	120.3	H25B—C25—H25C	109.5
C10—C11—H11	120.3	C7—N1—C1	115.58 (13)
C11—C12—C13	120.6 (2)	C7—N1—H1N	108.7 (12)
C11—C12—H12	119.7	C1—N1—H1N	106.8 (12)
C13—C12—H12	119.7	C14—O2—C22	119.78 (18)
C12—C13—C14	120.1 (2)	C16—O3—C24	118.36 (16)
N1—C1—C2—C8	54.66 (18)	C11—C12—C13—C14	0.5 (4)
C9—C1—C2—C8	176.83 (14)	C12—C13—C14—O2	179.8 (2)
N1—C1—C2—C3	−66.38 (19)	C12—C13—C14—C9	−0.4 (3)
C9—C1—C2—C3	55.80 (19)	C10—C9—C14—O2	179.74 (17)
C8—C2—C3—C4	−54.3 (2)	C1—C9—C14—O2	2.3 (2)
C1—C2—C3—C4	66.4 (2)	C10—C9—C14—C13	−0.1 (3)
C2—C3—C4—C5	45.8 (2)	C1—C9—C14—C13	−177.49 (17)
C2—C3—C4—C21	169.49 (17)	N1—C7—C15—C20	−17.0 (2)
C3—C4—C5—C6	−45.3 (2)	C6—C7—C15—C20	105.11 (19)
C21—C4—C5—C6	−169.20 (17)	N1—C7—C15—C16	166.35 (16)
C4—C5—C6—C8	52.7 (2)	C6—C7—C15—C16	−71.5 (2)
C4—C5—C6—C7	−66.8 (2)	C20—C15—C16—O3	179.34 (17)
C8—C6—C7—N1	−56.66 (17)	C7—C15—C16—O3	−3.9 (2)
C5—C6—C7—N1	63.43 (17)	C20—C15—C16—C17	0.0 (3)
C8—C6—C7—C15	−179.07 (14)	C7—C15—C16—C17	176.80 (16)
C5—C6—C7—C15	−58.98 (18)	O3—C16—C17—C18	−179.4 (2)
C3—C2—C8—O1	−117.4 (2)	C15—C16—C17—C18	−0.1 (3)
C1—C2—C8—O1	117.36 (19)	C16—C17—C18—C19	0.4 (4)
C3—C2—C8—C6	62.90 (18)	C17—C18—C19—C20	−0.7 (4)
C1—C2—C8—C6	−62.34 (18)	C16—C15—C20—C19	−0.2 (3)
C5—C6—C8—O1	118.6 (2)	C7—C15—C20—C19	−176.98 (18)
C7—C6—C8—O1	−116.67 (19)	C18—C19—C20—C15	0.6 (3)
C5—C6—C8—C2	−61.71 (19)	C15—C7—N1—C1	177.62 (14)
C7—C6—C8—C2	63.03 (18)	C6—C7—N1—C1	55.21 (18)
N1—C1—C9—C10	18.0 (2)	C9—C1—N1—C7	−176.73 (14)
C2—C1—C9—C10	−104.10 (19)	C2—C1—N1—C7	−53.93 (19)
N1—C1—C9—C14	−164.69 (16)	C13—C14—O2—C22	−4.1 (3)
C2—C1—C9—C14	73.2 (2)	C9—C14—O2—C22	176.08 (18)
C14—C9—C10—C11	0.4 (3)	C23—C22—O2—C14	−177.42 (19)
C1—C9—C10—C11	177.78 (18)	C17—C16—O3—C24	−18.1 (3)
C9—C10—C11—C12	−0.3 (3)	C15—C16—O3—C24	162.60 (17)
C10—C11—C12—C13	−0.1 (4)	C25—C24—O3—C16	−167.01 (19)