1-Methyl-2,4-bis­(2-methoxy­phen­yl)-3-aza­bicyclo­[3.3.1]nonan-9-one

P Parthiban; V Ramkumar; Yeon Tae Jeong

doi:10.1107/S1600536809047928

. 2009 Nov 18;65(Pt 12):o3103. doi: 10.1107/S1600536809047928

1-Methyl-2,4-bis(2-methoxyphenyl)-3-azabicyclo[3.3.1]nonan-9-one

P Parthiban ^a, V Ramkumar ^b, Yeon Tae Jeong ^a,^*

PMCID: PMC2972093 PMID: 21578830

Abstract

The crystal structure of the title compound, C₂₃H₂₇NO₃, shows that the compound exists in a chair–chair conformation with an equatorial disposition of 2-methoxyphenyl groups at an angle of 39.94 (3)° with respect to each other. An intermolecular N—H⋯π interaction is observed in the crystal packing.

Related literature

For the biological activity of 3-azabicyclononanes, see: Barker et al. (2005 ▶); Hardick et al. (1996 ▶); Jeyaraman & Avila (1981 ▶). For related structures with similar conformations, see: Parthiban et al. (2008 ▶); Parthiban, Ramkumar & Jeong (2009 ▶); Parthiban, Ramkumar, Kim et al. (2009 ▶). For a related structure with a chair–boat conformation, see: Smith-Verdier et al. (1983 ▶). For a related structure with a boat–boat conformation, see: Padegimas & Kovacic (1972 ▶). For ring puckering parameters, see: Cremer & Pople (1975 ▶); Nardelli (1983 ▶). graphic file with name e-65-o3103-scheme1.jpg

Experimental

Crystal data

C₂₃H₂₇NO₃
M _r = 365.46
Monoclinic,
a = 7.9569 (3) Å
b = 20.8291 (9) Å
c = 11.6708 (6) Å
β = 96.297 (2)°
V = 1922.59 (15) Å³
Z = 4
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 298 K
0.41 × 0.24 × 0.20 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1999 ▶) T _min = 0.288, T _max = 0.980
14049 measured reflections
4608 independent reflections
3166 reflections with I > 2σ(I)
R _int = 0.026

Refinement

R[F ² > 2σ(F ²)] = 0.048
wR(F ²) = 0.127
S = 1.02
4608 reflections
251 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.22 e Å⁻³
Δρ_min = −0.21 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 ▶) and Mercury (Macrae et al., 2006 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809047928/ez2190sup1.cif

e-65-o3103-sup1.cif^{(22.5KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809047928/ez2190Isup2.hkl

e-65-o3103-Isup2.hkl^{(225.8KB, hkl)}

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯Cg1ⁱ	0.862 (15)	2.852 (3)	3.6276 (14)	150.6 (12)

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Symmetry code: (i) Inline graphic . Cg1 is the centroid of the C16–C21 ring.

Acknowledgments

This research was supported by the Industrial Technology Devlopment Program, which was conducted by the Ministry of Knowledge Economy of the Korean Government. The authors acknowledge the Department of Chemistry, IIT Madras, for the X-ray data collection.

supplementary crystallographic information

Comment

3-Azabicyclononanes are an important class of heterocycles due to their broad spectrum biological activities (Jeyaraman & Avila, 1981; Hardick et al., 1996; Barker et al., 2005). Owing to the diverse possibilities in conformations, viz., chair-chair (Parthiban et al., 2008; Parthiban, Ramkumar & Jeong, 2009; Parthiban, Ramkumar, Kim et al., 2009), chair-boat (Smith-Verdier et al., 1983) and boat-boat (Padegimas & Kovacic, 1972) for the azabicycle, the present crystal study was undertaken to explore the conformation, stereochemistry and bonding of the title compound.

The analysis of torsion angles, asymmetry parameters and least-squares planes calculated for the title compound shows that the piperidine ring adopts a near ideal chair conformation with deviations of the ring atoms C8 and N1 from the C1/C2/C6/C7 plane by 0.655 (3) Å and -0.708 (3) Å, respectively. The smallest displacement asymmetry parameters are q2 = 0.0341 (15) Å and q3 =0.6123 (15) Å (Nardelli, 1983). The total puckering amplitude, Q_T = 0.6132 (15) Å and θ = 3.14 (14) ° (Cremer & Pople, 1975). The cyclohexane ring deviates from the ideal chair conformation by the deviation of ring atoms C4 and C8 from the C2/C3/C5/C6 plane by -0.697 (4) Å and 0.535 (3) Å, respectively. The smallest displacement asymmetry parameters are q2 = 0.1216 (17) Å and q3 = 0.5322 (17) Å (Nardelli, 1983); total puckering amplitude, Q_T = 0.5460 (16) Å, and θ =12.87 (18)° (Cremer & Pople, 1975). Hence, the title compound C₂₃H₂₇NO₃, exists in a chair-chair conformation with an equatorial orientation of the ortho-methoxyphenyl groups on the heterocycle, which are orientated at an angle of 39.94 (3)° with respect to each other. The crystal structure is stabilized by an intermolecular N-H···π interaction between N1-H1A and the C16/C17/C18/C19/C20/C21 ring in a neighbouring molecule [N···centroid distance of 2.852 (3)Å; symmetry operator: 1-x,-y,1-z].

Experimental

A mixture of 2-methylcyclohexanone (0.05 mol, 5.61 g) and ortho-methoxybenzaldehyde (0.1 mol, 13.62 g) was added to a warm solution of ammonium acetate (0.075 mol, 5.78 g) in 50 ml of absolute ethanol. The mixture was gently warmed with stirring until a yellow color was obtained during the mixing of the reactants and then allowed to stir at 303–308° K until formation of the product. At the end, the crude azabicyclic ketone was separated by filtration and washed with a 1:5 ethanol-ether mixture until the solid became colorless. Recrystallization of the compound from ethanol gave X-ray diffraction quality crystals of 1-methyl-2,4-bis(2-methoxyphenyl)-3- azabicyclo[3.3.1]nonan-9-one.