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

Parthiban, P.; Ramkumar, V.; Santan, H.D.; Kim, J.T.; Jeong, Y.T.

doi:10.1107/S1600536808024744

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 64| Part 9| September 2008| Page o1710

doi:10.1107/S1600536808024744

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

P. Parthiban,^a V. Ramkumar,^b H. D. Santan,^a Jong Tae Kim ^a and Yeon Tae Jeong ^a ^*

^aDivision of Image Science and Information Engineering, Pukyong National University, Busan 608 739, Republic of Korea, and ^bDepartment of Chemistry, IIT Madras, Chennai, Tamilnadu, India
^*Correspondence e-mail: ytjeong@pknu.ac.kr

(Received 15 July 2008; accepted 1 August 2008; online 6 August 2008)

In the title compound, C₂₀H₁₉F₂NO, a crystallographic mirror plane bisects the molecule, passing through the N, O and two C atoms of the central ring system. The molecule exists in a twin-chair conformation with equatorial dispositions of the 4-fluorophenyl groups on both sides of the secondary amino groups; the dihedral angle between the aromatic ring planes is 28.67 (3)°.

Related literature

For chemical background, see: Buxton & Roberts (1996 ); Evans & Seddon (1997 ); Ramachandran et al. (2007 ). For ring puckering parameters, see: Cremer & Pople (1975 ).

Experimental

Crystal data

C₂₀H₁₉F₂NO
M_r = 327.36
Orthorhombic, P n m a
a = 7.6153 (3) Å
b = 21.1392 (9) Å
c = 10.0878 (4) Å
V = 1623.95 (11) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 298 (2) K
0.35 × 0.32 × 0.30 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2004 ) T_min = 0.967, T_max = 0.971
11360 measured reflections
2064 independent reflections
1596 reflections with I > 2σ(I)
R_int = 0.020

Refinement

R[F² > 2σ(F²)] = 0.041
wR(F²) = 0.141
S = 0.91
2064 reflections
118 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.19 e Å⁻³

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

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808024744/hb2763sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808024744/hb2763Isup2.hkl

checkCIF report

Comment top

Fluorine substituted organic compounds are very impotant due to the significance of C—F bonds in some bioorganic systems (e.g. Evans & Seddon, 1997). The intermolecular and intramolecular hydrogen bonds involving fluorine atom have attracted much attention in various aspects (e.g. Ramachandran et al., 2007). Moreover, the biological activities mainly depend on the stereochemistry of the synthesized compound (e.g. Buxton & Roberts, 1996). Hence, realising the importance of the investigation of the conformation, stereochemistry and the nature of bondings in the synthesized title fluorine substituted heterocycle, (I), we have carried out single-crystal X-ray diffraction studies.

An analysis of torsion angles, asymmetry parameters and least-squares plane calculation shows that the piperidine ring adopts a near ideal chair conformation with the deviation of ring atoms N1 and C5 from the C1/C1ⁱ/C2/C2ⁱ (i = x, 1/2-y, z) plane by -0.670 (3)Å and 0.693 (3)Å respectively, Q_T = 0.6064 (13) Å. The cyclohexane ring deviate from the ideal chair conformation by the deviation of ring atoms C4 and C5 from the C2/C2ⁱ/C3/C3ⁱ plane by 0.522 (4)Å and 0.734 (3)Å respectively, Q_T = 0.5681 (14)Å (Cremer & Pople, 1975).

Compound (I) has a crystallographic mirror plane, which bisects the molecule passing through N1, C4, C5 and O1 of the central ring (Fig. 1) and exists in twin-chair conformation with equatorial orientations of the para fluoro phenyl groups on the heterocycle with the torsion angle of C5—C2—C1—C6 is 178.41 (6)°. The aryl groups are orientated at an angle of 28.67 (3)° to each other.

Related literature top

For chemical background, see: Buxton & Roberts (1996); Evans & Seddon (1997); Ramachandran et al. (2007). For ring puckering paramaters, see: Cremer & Pople (1975).

Experimental top

A mixture of cyclohexanone (0.05 mol) and para fluorobenzaldehyde (0.1 mol) was added to a warm solution of ammonium acetate (0.075 mol) in 50 ml of absolute ethanol. The mixture was very gently warmed on a hot plate till the yellow color formed during the mixing of the reactants and allowed to stir till the formation of the product. Thus, the formed azabicyclononane was separated by filtration and washed with a 1:5 v/v ethanol-ether mixture till the solid became colorless. Then, recrystallization of the compound from ethanol afforded colorless blocks of (I).

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (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 (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of (I) with non-hydrogen atoms represented as 30% probability ellipsoids.

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

Crystal data top

C₂₀H₁₉F₂NO	F(000) = 688
M_r = 327.36	D_x = 1.339 Mg m⁻³
Orthorhombic, Pnma	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2n	Cell parameters from 4451 reflections
a = 7.6153 (3) Å	θ = 3.4–28.0°
b = 21.1392 (9) Å	µ = 0.10 mm⁻¹
c = 10.0878 (4) Å	T = 298 K
V = 1623.95 (11) Å³	Block, colourless
Z = 4	0.35 × 0.32 × 0.30 mm

Data collection top

Bruker APEXII CCD diffractometer	2064 independent reflections
Radiation source: fine-focus sealed tube	1596 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.020
ω scans	θ_max = 28.3°, θ_min = 1.9°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −8→10
T_min = 0.967, T_max = 0.971	k = −28→28
11360 measured reflections	l = −13→12

Refinement top

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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.141	H atoms treated by a mixture of independent and constrained refinement
S = 0.91	w = 1/[σ²(F_o²) + (0.0897P)² + 0.3733P] where P = (F_o² + 2F_c²)/3
2064 reflections	(Δ/σ)_max < 0.001
118 parameters	Δρ_max = 0.22 e Å⁻³
0 restraints	Δρ_min = −0.19 e Å⁻³

Crystal data top

C₂₀H₁₉F₂NO	V = 1623.95 (11) Å³
M_r = 327.36	Z = 4
Orthorhombic, Pnma	Mo Kα radiation
a = 7.6153 (3) Å	µ = 0.10 mm⁻¹
b = 21.1392 (9) Å	T = 298 K
c = 10.0878 (4) Å	0.35 × 0.32 × 0.30 mm

Data collection top

Bruker APEXII CCD diffractometer	2064 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2004)	1596 reflections with I > 2σ(I)
T_min = 0.967, T_max = 0.971	R_int = 0.020
11360 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.041	0 restraints
wR(F²) = 0.141	H atoms treated by a mixture of independent and constrained refinement
S = 0.91	Δρ_max = 0.22 e Å⁻³
2064 reflections	Δρ_min = −0.19 e Å⁻³
118 parameters

Special details top

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 taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
C1	0.92315 (17)	0.30735 (5)	0.39201 (12)	0.0391 (3)
H1	0.8839	0.3055	0.2996	0.047*
C2	0.75726 (16)	0.30901 (5)	0.48153 (14)	0.0421 (3)
H2	0.6864	0.3460	0.4576	0.051*
C3	0.79266 (19)	0.31054 (6)	0.63140 (13)	0.0473 (3)
H3A	0.8701	0.3458	0.6508	0.057*
H3B	0.6827	0.3181	0.6773	0.057*
C4	0.8751 (3)	0.2500	0.68562 (18)	0.0492 (4)
H4A	0.9993	0.2500	0.6644	0.059*
H4B	0.8642	0.2500	0.7814	0.059*
C5	0.6527 (2)	0.2500	0.45348 (18)	0.0435 (4)
C6	1.03437 (17)	0.36590 (5)	0.40791 (12)	0.0400 (3)
C7	0.9916 (2)	0.41937 (6)	0.33533 (16)	0.0543 (4)
H7	0.8976	0.4179	0.2766	0.065*
C8	1.0856 (2)	0.47481 (7)	0.34848 (19)	0.0666 (5)
H8	1.0550	0.5107	0.3003	0.080*
C9	1.2238 (2)	0.47573 (7)	0.4334 (2)	0.0643 (5)
C10	1.2733 (2)	0.42414 (8)	0.50616 (19)	0.0641 (4)
H10	1.3688	0.4261	0.5634	0.077*
C11	1.1771 (2)	0.36882 (7)	0.49220 (15)	0.0519 (4)
H11	1.2091	0.3331	0.5404	0.062*
F1	1.31755 (17)	0.53023 (5)	0.44594 (17)	0.1030 (5)
H111	1.121 (3)	0.2500	0.369 (2)	0.047 (5)*
N1	1.0241 (2)	0.2500	0.41923 (15)	0.0384 (3)
O1	0.50237 (19)	0.2500	0.41536 (17)	0.0626 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0441 (7)	0.0372 (6)	0.0359 (6)	0.0013 (5)	−0.0009 (5)	0.0021 (4)
C2	0.0395 (6)	0.0368 (6)	0.0500 (7)	0.0045 (5)	−0.0010 (5)	0.0018 (5)
C3	0.0493 (7)	0.0465 (7)	0.0461 (7)	−0.0017 (6)	0.0077 (6)	−0.0072 (5)
C4	0.0529 (10)	0.0585 (10)	0.0361 (9)	0.000	0.0003 (8)	0.000
C5	0.0384 (9)	0.0483 (9)	0.0437 (9)	0.000	−0.0027 (7)	0.000
C6	0.0440 (7)	0.0352 (5)	0.0406 (6)	0.0016 (5)	0.0073 (5)	0.0021 (4)
C7	0.0567 (8)	0.0455 (7)	0.0605 (8)	0.0048 (6)	0.0044 (7)	0.0137 (6)
C8	0.0694 (10)	0.0390 (7)	0.0915 (12)	0.0051 (7)	0.0242 (10)	0.0157 (7)
C9	0.0586 (9)	0.0382 (7)	0.0961 (13)	−0.0091 (6)	0.0292 (9)	−0.0104 (7)
C10	0.0558 (9)	0.0579 (9)	0.0787 (11)	−0.0105 (7)	0.0011 (8)	−0.0110 (8)
C11	0.0529 (8)	0.0455 (7)	0.0572 (8)	−0.0038 (6)	−0.0029 (6)	0.0043 (6)
F1	0.0834 (8)	0.0474 (6)	0.1782 (14)	−0.0225 (5)	0.0323 (8)	−0.0170 (6)
N1	0.0377 (8)	0.0341 (7)	0.0434 (8)	0.000	0.0057 (6)	0.000
O1	0.0421 (8)	0.0693 (10)	0.0763 (11)	0.000	−0.0159 (7)	0.000

Geometric parameters (Å, º) top

C1—N1	1.4613 (14)	C5—C2ⁱ	1.5067 (15)
C1—C6	1.5083 (16)	C6—C11	1.381 (2)
C1—C2	1.5533 (18)	C6—C7	1.3856 (17)
C1—H1	0.9800	C7—C8	1.380 (2)
C2—C5	1.5067 (15)	C7—H7	0.9300
C2—C3	1.536 (2)	C8—C9	1.357 (3)
C2—H2	0.9800	C8—H8	0.9300
C3—C4	1.5266 (17)	C9—F1	1.3613 (17)
C3—H3A	0.9700	C9—C10	1.367 (3)
C3—H3B	0.9700	C10—C11	1.387 (2)
C4—C3ⁱ	1.5266 (17)	C10—H10	0.9300
C4—H4A	0.9700	C11—H11	0.9300
C4—H4B	0.9700	N1—C1ⁱ	1.4613 (14)
C5—O1	1.208 (2)	N1—H111	0.89 (2)

N1—C1—C6	111.44 (10)	O1—C5—C2	124.12 (7)
N1—C1—C2	109.70 (10)	O1—C5—C2ⁱ	124.12 (7)
C6—C1—C2	112.11 (9)	C2—C5—C2ⁱ	111.76 (14)
N1—C1—H1	107.8	C11—C6—C7	118.28 (12)
C6—C1—H1	107.8	C11—C6—C1	122.96 (11)
C2—C1—H1	107.8	C7—C6—C1	118.76 (12)
C5—C2—C3	107.16 (11)	C8—C7—C6	121.34 (15)
C5—C2—C1	107.58 (11)	C8—C7—H7	119.3
C3—C2—C1	115.47 (11)	C6—C7—H7	119.3
C5—C2—H2	108.8	C9—C8—C7	118.37 (14)
C3—C2—H2	108.8	C9—C8—H8	120.8
C1—C2—H2	108.8	C7—C8—H8	120.8
C4—C3—C2	114.02 (11)	C8—C9—F1	118.51 (16)
C4—C3—H3A	108.7	C8—C9—C10	122.75 (14)
C2—C3—H3A	108.7	F1—C9—C10	118.74 (18)
C4—C3—H3B	108.7	C9—C10—C11	118.19 (16)
C2—C3—H3B	108.7	C9—C10—H10	120.9
H3A—C3—H3B	107.6	C11—C10—H10	120.9
C3ⁱ—C4—C3	113.91 (16)	C6—C11—C10	121.05 (14)
C3ⁱ—C4—H4A	108.8	C6—C11—H11	119.5
C3—C4—H4A	108.8	C10—C11—H11	119.5
C3ⁱ—C4—H4B	108.8	C1ⁱ—N1—C1	112.11 (14)
C3—C4—H4B	108.8	C1ⁱ—N1—H111	109.1 (7)
H4A—C4—H4B	107.7	C1—N1—H111	109.1 (7)

N1—C1—C2—C5	−58.02 (14)	C2—C1—C6—C7	−84.10 (15)
C6—C1—C2—C5	177.61 (10)	C11—C6—C7—C8	−1.5 (2)
N1—C1—C2—C3	61.57 (13)	C1—C6—C7—C8	178.21 (13)
C6—C1—C2—C3	−62.80 (13)	C6—C7—C8—C9	0.9 (2)
C5—C2—C3—C4	52.64 (16)	C7—C8—C9—F1	179.55 (15)
C1—C2—C3—C4	−67.17 (15)	C7—C8—C9—C10	0.0 (3)
C2—C3—C4—C3ⁱ	−43.3 (2)	C8—C9—C10—C11	−0.2 (3)
C3—C2—C5—O1	113.4 (2)	F1—C9—C10—C11	−179.77 (15)
C1—C2—C5—O1	−121.84 (19)	C7—C6—C11—C10	1.3 (2)
C3—C2—C5—C2ⁱ	−65.39 (17)	C1—C6—C11—C10	−178.44 (14)
C1—C2—C5—C2ⁱ	59.35 (18)	C9—C10—C11—C6	−0.4 (2)
N1—C1—C6—C11	−27.77 (17)	C6—C1—N1—C1ⁱ	−174.53 (8)
C2—C1—C6—C11	95.62 (15)	C2—C1—N1—C1ⁱ	60.72 (16)
N1—C1—C6—C7	152.51 (13)

Symmetry code: (i) x, −y+1/2, z.

Experimental details

Crystal data
Chemical formula	C₂₀H₁₉F₂NO
M_r	327.36
Crystal system, space group	Orthorhombic, Pnma
Temperature (K)	298
a, b, c (Å)	7.6153 (3), 21.1392 (9), 10.0878 (4)
V (Å³)	1623.95 (11)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.35 × 0.32 × 0.30

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2004)
T_min, T_max	0.967, 0.971
No. of measured, independent and observed [I > 2σ(I)] reflections	11360, 2064, 1596
R_int	0.020
(sin θ/λ)_max (Å⁻¹)	0.668

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.141, 0.91
No. of reflections	2064
No. of parameters	118
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.22, −0.19

Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997).

Acknowledgements

This research was supported by the second stage of the BK 21 program and Pukyong National University under the 2008 Postdoc program.

References

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