2,4,6,8-Tetra­kis(4-fluoro­phen­yl)-3,7-diaza­bicyclo­[3.3.1]nonan-9-one

S Natarajan; V Sudhapriya; V Vijayakumar; N Shoba; J Suresh; P L Nilantha Lakshman

doi:10.1107/S1600536808039135

. 2008 Nov 29;64(Pt 12):o2496. doi: 10.1107/S1600536808039135

2,4,6,8-Tetrakis(4-fluorophenyl)-3,7-diazabicyclo[3.3.1]nonan-9-one

S Natarajan ^a, V Sudhapriya ^b, V Vijayakumar ^b, N Shoba ^c, J Suresh ^c, P L Nilantha Lakshman ^d,^*

PMCID: PMC2960046 PMID: 21581457

Abstract

In the title compound, C₃₁H₂₄F₄N₂O, the bicyclo[3.3.1]nonane ring exists in a chair-boat conformation. Two of the four fluorine-substituted rings adopt equatorial dispositions with the piperidin-4-one rings. Molecules are linked into a two-dimensional network parallel to ( Inline graphic 01) by N—H⋯O, C—H⋯F and C—H⋯O hydrogen bonds. Intermolecular N—H⋯π and C—H⋯π interactions are also observed.

Related literature

For general background, see: Asakawa (1995 ▶); Jeyaraman & Avila (1981 ▶).

Experimental

Crystal data

C₃₁H₂₄F₄N₂O
M _r = 516.52
Monoclinic,
a = 37.1521 (9) Å
b = 7.1458 (5) Å
c = 26.2165 (7) Å
β = 133.249 (4)°
V = 5069.5 (4) Å³
Z = 8
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 293 (2) K
0.19 × 0.16 × 0.11 mm

Data collection

Nonius MACH-3 diffractometer
Absorption correction: ψ scan (North et al., 1968 ▶) T _min = 0.986, T _max = 0.991
5315 measured reflections
4465 independent reflections
2735 reflections with I > 2σ(I)
R _int = 0.024
2 standard reflections frequency: 60 min intensity decay: none

Refinement

R[F ² > 2σ(F ²)] = 0.039
wR(F ²) = 0.112
S = 1.02
4465 reflections
351 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.14 e Å⁻³
Δρ_min = −0.23 e Å⁻³

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994 ▶); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1996 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: PLATON (Spek, 2003 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808039135/ci2727sup1.cif

e-64-o2496-sup1.cif^{(25.9KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808039135/ci2727Isup2.hkl

e-64-o2496-Isup2.hkl^{(214.4KB, 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
C15—H15⋯F4ⁱ	0.93	2.52	3.254 (3)	136
C3—H3⋯O1ⁱⁱ	0.98	2.56	3.358 (2)	138
N2—H1A⋯O1ⁱⁱⁱ	0.86 (2)	2.53 (2)	3.292 (2)	148 (3)
N1—H2A⋯Cg3^iv	0.89 (2)	2.70 (3)	3.549 (3)	160 (2)
C36—H36⋯Cg2^v	0.93	2.81	3.696 (3)	160
C42—H42⋯Cg1^v	0.93	2.78	3.651 (3)	157
C45—H45⋯Cg3ⁱⁱⁱ	0.93	2.65	3.494 (3)	151

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) ; (v) . Cg1, Cg2 and Cg3 are the centroids of the C31–C36, C41–C46 and C61–C66 rings, respectively.

Acknowledgments

SN thanks the DST for the FIST programme.

supplementary crystallographic information

Comment

Azabicyclononane and their derivatives are studied intensively because of their pharmaceutical use and their application as an important structure in the field of molecular recognition. The 3-azabicyclo[3.3.1] nonane skeletal system easily constructed via a double Mannich reaction (Jeyaraman & Avila, 1981), has been known for some time. The bicyclo[3.3.1]nonane carbon framework is frequently encountered in natural products, in particular in alkaloids and terpenoids, e.g. trifarienols (Asakawa, 1995). Further, the study of conformation of the bicyclic ring helps in the understanding of interactions that are possible between the substituted aryl rings.

The molecular structure of the title compound is shown in Fig.1. The bicyclic [3.3.1]nonane ring can exist in chair-chair, chair-boat and boat-boat conformations. Among these, the chair-chair conformation is the most favourable. In the title compound, the bicyclic ring system adopts a chair-boat conformation. In the N1-piperidine ring of the compound, atoms N1 and C7 deviate from the C1/C2/C5/C6 plane by 0.652 (3) and 0.685 (3) Å, respectively, indicating a nearly ideal boat conformation. The phenyl rings substituted at C1 and C6 positions are oriented at an angle of 28.2 (1)° to each other. The phenyl rings substituted at C3 and C4 are oriented with an angle of 28.6 (1)° between them and they are equatorially disposed with respect to the piperidine ring, with torsion angles C7—C5—C4—C41 = -175.1 (2)° and C7—C2—C3—C31 = 173.3 (2)°.

Fig. 2 shows the packing viewed down the c axis. Pairs of intermolecular C—H···F (Table 1) hydrogen bonds form centrosymmetric R₂²(24) dimers. The moelcules are linked into a two-dimensional network parallel to the (101) by N—H···O, C—H···F and C—H···O hydrogen bonds. In addition, some C—H···π interactions (Table 1 ; Cg1, Cg2 and Cg3 refer to centroids of C31-C36, C41-C46 and C61-C66 rings, respectively).

Experimental

A mixture of 0.73 ml of dry acetone (0.01 mol), 4.96 ml of 4-fluorobenzaldehyde (0.04 mol), 1.54 g dry ammonium acetate (0.02 mol) were taken in a flask with ethanol as solvent. Contents were heated with constant shaking until it becomes pale orange in colour. Then the contents were kept aside for 24 h and the title compound was filtered through the Buchner funnel, washed with 1:1 ethanol-ether mixture until the yellow colour disappeared and dried (yield 45%, m.p. 484 K).