2,4-Bis(4-chloro­phen­yl)-3-aza­bicyclo­[3.3.1]nonan-9-one

P Parthiban; V Ramkumar; Min Sung Kim; S Kabilan; Yeon Tae Jeong

doi:10.1107/S160053680900590X

. 2009 Feb 25;65(Pt 3):o609. doi: 10.1107/S160053680900590X

2,4-Bis(4-chlorophenyl)-3-azabicyclo[3.3.1]nonan-9-one

P Parthiban ^a, V Ramkumar ^b, Min Sung Kim ^a, S Kabilan ^c, Yeon Tae Jeong ^a,^*

PMCID: PMC2968690 PMID: 21582262

Abstract

In the molecular structure of the title compound, C₂₀H₁₉Cl₂NO, the molecule exists in a twin-chair conformation with equatorial dispositions of the 4-chlorophenyl groups on both sides of the secondary amino group; the dihedral angle between the aromatic ring planes is 31.33 (3)°. The crystal structure is stabilized by N—H⋯O interactions, leading to chains of molecules.

Related literature

For the biological activity of diterpenoid/norditerpenoid alkaloids, see: Hardick et al. (1996 ▶); Jeyaraman et al. (1981 ▶). For similiar structures, see: Parthiban et al. (2008a ▶,b ▶,c ▶,d ▶,e ▶). For puckering parameters, see: Cremer & Pople (1975 ▶).

Experimental

Crystal data

C₂₀H₁₉Cl₂NO
M _r = 360.26
Monoclinic,
a = 16.2589 (4) Å
b = 6.8983 (2) Å
c = 18.1291 (5) Å
β = 116.149 (1)°
V = 1825.23 (9) Å³
Z = 4
Mo Kα radiation
μ = 0.36 mm⁻¹
T = 298 K
0.42 × 0.38 × 0.25 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1999 ▶) T _min = 0.863, T _max = 0.915
15050 measured reflections
4997 independent reflections
3241 reflections with I > 2σ(I)
R _int = 0.021

Refinement

R[F ² > 2σ(F ²)] = 0.046
wR(F ²) = 0.135
S = 1.02
4997 reflections
221 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.38 e Å⁻³
Δρ_min = −0.42 e Å⁻³

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: SAINT-Plus (Bruker, 2004 ▶); data reduction: SAINT-Plus; 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.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053680900590X/bq2124sup1.cif

e-65-0o609-sup1.cif^{(20.7KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S160053680900590X/bq2124Isup2.hkl

e-65-0o609-Isup2.hkl^{(244.8KB, 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⋯O1ⁱ	0.85 (2)	2.31 (2)	3.1202 (18)	160.2 (18)

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Symmetry code: (i) Inline graphic .

Acknowledgments

The authors acknowledge the Department of Chemistry, IIT Madras, for the X-ray data collection.

supplementary crystallographic information

Comment

The widespread diterpenoid/norditerpenoid alkaloids posses the 3-azabicyclo [3.3.1]nonane pharmacophore, and as a consequence, the above alkaloids having broad spectrum of biological activities (Jeyaraman et al., 1981; Hardick et al., 1996). Hence, the synthesis and stereochemistry of 3-azabicyclononan-9-ones are more important in recent days (Parthiban et al., 2008a,b,c,d,e). A study of torsion angles, asymmetry parameters and least-squares plane calculation shows that the piperidine ring adopts near ideal chair conformation with the deviation of ring atoms N1 and C8 from the C1/C2/C6/C7 plane by -0.642 (3)Å and 0.712 (3)Å, respectively, Q_T=0.607 (2)Å, q(2)=0.044 (2)Å and q(3)=-0.606 (2)Å, θ=175.8 (2)°. whereas the cyclohexane ring deviate from the ideal chair conformation; the cyclohexane atoms C4 and C8 deviate from the C2/C3/C5/C6 plane by -0.557 (2)Å and 0.710 (3)Å, respectively, Q_T=0.560 (2) Å, q(2)=0.117 (2)Å and, q(3)=-0.548 (2)Å, θ=167.9 (2)°. (Cremer & Pople, 1975). Hence, the title compound C₂₀H₁₉Cl₂NO, exists in double chair conformation with equatorial dispositions of the para chlorophenyl groups with the torsion angles of C8—C2—C1—C9 and C8—C6—C7—C15 are 177.88 (4)° and -179.01 (4)°, respectively. The aryl groups are oriented at an angle of 31.33 (3)° to each other.

Experimental

In a warm solution of ammonium acetate (0.075 mol) in 50 ml of absolute ethanol, a mixture of cyclohexanone (0.05 mol) and para chlorobenzaldehyde (0.1 mol) was added and gently warmed with stirring on a hot plate till the yellow color was formed during the mixing of the reactants and cooled to room temperature. Then 50 ml of ether was added and allowed to stir over night at room temperature. Thus the obtained crude azabicyclic ketone was separated by filtration and washed with 1:5 ethanol-ether mixture till the solid became colorless. Recrystallization of the compound from ethanol gave X-ray diffraction quality crystals of 2,4-bis(4-chlorophenyl)-3-azabicyclo[3.3.1]nonan-9-one.