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

Parthiban, P.; Ramkumar, V.; Kim, M.S.; Lim, K.T.; Jeong, Y.T.

doi:10.1107/S1600536808036660

organic compounds

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ISSN: 2056-9890

Volume 64| Part 12| December 2008| Page o2332

doi:10.1107/S1600536808036660

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

P. Parthiban,^a V. Ramkumar,^b Min Sung Kim,^a Kwon Taek Lim ^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 6 November 2008; accepted 7 November 2008; online 13 November 2008)

The complete molecule of the title compound, C₂₀H₁₉Br₂NO, is generated by crystallographic mirror symmetry, with two C, one O and one N atom lying on the mirror plane. The compound exists in a twin-chair conformation with equatorial dispositions of the 3-bromophenyl groups [dihedral angle between rings = 27.37 (3)°]. The packing is stabilized by weak N—H⋯O and C—H⋯O interactions.

Related literature

For background, see: Barker et al. (2005 ); Jeyaraman & Avila (1981 ); Padegimas & Kovacic (1972 ); Smith-Verdier et al. (1983 ). For a similiar structure, see: Parthiban et al. (2008 ). For puckering parameters, see: Cremer & Pople (1975 ); Web & Becker (1967 ).

Experimental

Crystal data

C₂₀H₁₉Br₂NO
M_r = 449.18
Orthorhombic, P n m a
a = 7.1595 (6) Å
b = 24.5891 (19) Å
c = 10.2598 (6) Å
V = 1806.2 (2) Å³
Z = 4
Mo Kα radiation
μ = 4.49 mm⁻¹
T = 298 (2) K
0.34 × 0.25 × 0.18 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1999 ) T_min = 0.310, T_max = 0.498 (expected range = 0.277–0.445)
12758 measured reflections
2286 independent reflections
1554 reflections with I > 2σ(I)
R_int = 0.035

Refinement

R[F² > 2σ(F²)] = 0.042
wR(F²) = 0.103
S = 1.05
2286 reflections
118 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.84 e Å⁻³
Δρ_min = −0.71 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O1ⁱ	0.87 (5)	2.41 (5)	3.168 (5)	145 (4)
C1—H1⋯O1ⁱⁱ	0.98	2.54	3.361 (4)	142
Symmetry codes: (i) x-1, y, z; (ii) $[x-{\script{1\over 2}}, -y+{\script{3\over 2}}, -z+{\script{5\over 2}}]$ .

Data collection: SMART (Bruker, 1999); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808036660/hb2838sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808036660/hb2838Isup2.hkl

checkCIF report

Comment top

Azabicyclic ketones are an important class of heterocycles due to their broad-spectrum biological activities (Jeyaraman & Avila, 1981; Barker et al., 2005). Owing to the diverse possibilities in conformations, viz., chair-chair (Parthiban et al., 2008), 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 bondings in the title compound, (I).

The piperidine ring in (I) adopts an ideal chair conformation with the deviation of ring atoms C3 and N1 from the C1/C2/C2ⁱ/C1ⁱ (i = x, 3/2-y, z) plane being 0.686 (3) and -0.702 (3) Å, respectively. The q2 and q3 values are 0.010 (3) and -0.617 (3)Å and the total puckering amplitude, Q_T = 0.617 (3)Å and θ = 180.0 (3)° (Cremer & Pople, 1975; Web & Becker, 1967).

The cyclohexane ring deviate from the ideal chair conformation by the deviation of ring atoms C3 and C5 from the C2/C4/C4ⁱ/C2ⁱ plane by -0.725 (4) and 0.525 (3)Å, respectively. For the cyclohexane, the q2 and q3 parameters are 0.150 (4) and 0.543 (4)Å respectively. The total puckering amplitude, Q_T = 0.563 (3)Å and θ =15.6 (4)°. Hence, the title compound, exists in a twin-chair conformation with equatorial orientations of the 3-bromophenyl groups on the heterocycle, which are orientated at an angle of 27.37 (3)° to each other. The torsion angles of C3—C2—C1—C6 and its mirror plane C3—C2ⁱ—C1ⁱ—C6ⁱ is 174.45 (4)°. The packing is stabilized by weak N—H···O and C—H···O bonds (Table 1).

Related literature top

For background, see: Barker et al. (2005); Jeyaraman & Avila (1981); Padegimas & Kovacic (1972); Smith-Verdier et al. (1983); Web et al. (1967). For a similiar structure, see: Parthiban et al. (2008). For puckering parameters, see: Cremer & Pople (1975).

Experimental top

0.1 mol of meta Bromobenzaldehyde and 0.05 mol of cyclohexanone were simultaneously added to a warm solution of 0.075 mol ammonium acetate in 50 ml of absolute ethanol. The mixture was gently warmed on a hot plate till the yellow colour 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 warm condition (303–305 K). At the end, the crude azabicyclic ketone was separated by filtration and washed with 1:5 v/v ethanol-ether mixture until the solid become colourless. Colourless blocks of (I) were recrystallised from acetone.

Computing details top

Data collection: SMART (Bruker, 1999); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of (I) with non-hydrogen atoms represented as 30% probability ellipsoids.
	Fig. 2. Packing diagram with N—H···O (blue) and C—H···O (red) interactions.

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

Crystal data top

C₂₀H₁₉Br₂NO	F(000) = 896
M_r = 449.18	D_x = 1.652 Mg m⁻³
Orthorhombic, Pnma	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2n	Cell parameters from 3647 reflections
a = 7.1595 (6) Å	θ = 3.2–23.5°
b = 24.5891 (19) Å	µ = 4.49 mm⁻¹
c = 10.2598 (6) Å	T = 298 K
V = 1806.2 (2) Å³	Block, colourless
Z = 4	0.34 × 0.25 × 0.18 mm

Data collection top

Bruker SMART CCD diffractometer	2286 independent reflections
Radiation source: fine-focus sealed tube	1554 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.035
ω scans	θ_max = 28.9°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 1999)	h = −9→9
T_min = 0.310, T_max = 0.498	k = −33→33
12758 measured reflections	l = −13→9

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)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.103	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ²(F_o²) + (0.0338P)² + 2.5194P] where P = (F_o² + 2F_c²)/3
2286 reflections	(Δ/σ)_max < 0.001
118 parameters	Δρ_max = 0.84 e Å⁻³
0 restraints	Δρ_min = −0.71 e Å⁻³

Crystal data top

C₂₀H₁₉Br₂NO	V = 1806.2 (2) Å³
M_r = 449.18	Z = 4
Orthorhombic, Pnma	Mo Kα radiation
a = 7.1595 (6) Å	µ = 4.49 mm⁻¹
b = 24.5891 (19) Å	T = 298 K
c = 10.2598 (6) Å	0.34 × 0.25 × 0.18 mm

Data collection top

Bruker SMART CCD diffractometer	2286 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 1999)	1554 reflections with I > 2σ(I)
T_min = 0.310, T_max = 0.498	R_int = 0.035
12758 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.042	0 restraints
wR(F²) = 0.103	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	Δρ_max = 0.84 e Å⁻³
2286 reflections	Δρ_min = −0.71 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
Br1	0.06375 (6)	0.580496 (16)	0.86233 (5)	0.07173 (19)
C1	0.5903 (4)	0.70119 (11)	1.1050 (3)	0.0328 (6)
H1	0.6284	0.7040	1.1965	0.039*
C2	0.7711 (4)	0.69950 (12)	1.0210 (3)	0.0353 (6)
H2	0.8451	0.6677	1.0462	0.042*
C3	0.8806 (6)	0.7500	1.0506 (4)	0.0332 (9)
C4	0.7389 (4)	0.69827 (13)	0.8727 (3)	0.0401 (7)
H4A	0.8577	0.6919	0.8298	0.048*
H4B	0.6577	0.6679	0.8521	0.048*
C5	0.6529 (6)	0.7500	0.8173 (4)	0.0418 (10)
H5A	0.6685	0.7500	0.7234	0.050*
H5B	0.5200	0.7500	0.8356	0.050*
C6	0.4822 (4)	0.64879 (11)	1.0899 (3)	0.0350 (6)
C7	0.3394 (4)	0.64162 (11)	1.0003 (3)	0.0376 (7)
H7	0.2983	0.6707	0.9498	0.045*
C8	0.2582 (4)	0.59064 (12)	0.9868 (3)	0.0431 (8)
C9	0.3157 (5)	0.54686 (12)	1.0597 (4)	0.0541 (9)
H9	0.2610	0.5129	1.0488	0.065*
C10	0.4556 (6)	0.55456 (15)	1.1489 (4)	0.0621 (11)
H10	0.4955	0.5254	1.1996	0.074*
C11	0.5382 (5)	0.60472 (14)	1.1647 (4)	0.0511 (9)
H11	0.6324	0.6091	1.2262	0.061*
N1	0.4821 (5)	0.7500	1.0736 (3)	0.0303 (7)
O1	1.0403 (4)	0.7500	1.0910 (3)	0.0493 (8)
H1A	0.376 (6)	0.7500	1.115 (4)	0.033 (12)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0813 (3)	0.0450 (2)	0.0889 (4)	−0.01841 (19)	−0.0190 (2)	−0.0091 (2)
C1	0.0371 (15)	0.0305 (14)	0.0308 (16)	0.0038 (12)	0.0021 (12)	0.0031 (12)
C2	0.0324 (15)	0.0331 (14)	0.0404 (16)	0.0064 (12)	0.0004 (12)	0.0023 (13)
C3	0.030 (2)	0.045 (2)	0.025 (2)	0.000	0.0024 (16)	0.000
C4	0.0390 (16)	0.0432 (17)	0.0382 (17)	−0.0025 (13)	0.0047 (13)	−0.0087 (14)
C5	0.039 (2)	0.058 (3)	0.028 (2)	0.000	0.0000 (19)	0.000
C6	0.0401 (16)	0.0260 (13)	0.0387 (16)	0.0037 (12)	0.0105 (13)	0.0017 (12)
C7	0.0434 (17)	0.0247 (14)	0.0447 (18)	0.0012 (12)	0.0046 (14)	0.0023 (13)
C8	0.0480 (18)	0.0284 (15)	0.0531 (19)	−0.0031 (13)	0.0108 (16)	−0.0070 (14)
C9	0.066 (2)	0.0213 (14)	0.075 (3)	−0.0032 (15)	0.016 (2)	0.0009 (16)
C10	0.071 (3)	0.0344 (18)	0.081 (3)	0.0068 (17)	−0.001 (2)	0.0204 (19)
C11	0.054 (2)	0.0394 (18)	0.060 (2)	0.0025 (15)	−0.0034 (17)	0.0154 (16)
N1	0.0286 (17)	0.0237 (16)	0.0385 (19)	0.000	0.0056 (15)	0.000
O1	0.0322 (17)	0.064 (2)	0.0520 (19)	0.000	−0.0072 (14)	0.000

Geometric parameters (Å, º) top

Br1—C8	1.905 (3)	C5—H5A	0.9700
C1—N1	1.464 (3)	C5—H5B	0.9700
C1—C6	1.511 (4)	C6—C7	1.386 (4)
C1—C2	1.555 (4)	C6—C11	1.387 (4)
C1—H1	0.9800	C7—C8	1.389 (4)
C2—C3	1.500 (4)	C7—H7	0.9300
C2—C4	1.540 (4)	C8—C9	1.374 (5)
C2—H2	0.9800	C9—C10	1.369 (5)
C3—O1	1.216 (5)	C9—H9	0.9300
C3—C2ⁱ	1.500 (4)	C10—C11	1.377 (5)
C4—C5	1.523 (4)	C10—H10	0.9300
C4—H4A	0.9700	C11—H11	0.9300
C4—H4B	0.9700	N1—C1ⁱ	1.464 (3)
C5—C4ⁱ	1.523 (4)	N1—H1A	0.87 (5)

N1—C1—C6	113.9 (2)	C4ⁱ—C5—H5B	108.9
N1—C1—C2	109.9 (2)	C4—C5—H5B	108.9
C6—C1—C2	110.3 (2)	H5A—C5—H5B	107.7
N1—C1—H1	107.5	C7—C6—C11	118.8 (3)
C6—C1—H1	107.5	C7—C6—C1	123.7 (3)
C2—C1—H1	107.5	C11—C6—C1	117.4 (3)
C3—C2—C4	107.1 (3)	C6—C7—C8	119.3 (3)
C3—C2—C1	107.5 (2)	C6—C7—H7	120.3
C4—C2—C1	115.1 (2)	C8—C7—H7	120.3
C3—C2—H2	109.0	C9—C8—C7	121.8 (3)
C4—C2—H2	109.0	C9—C8—Br1	118.8 (2)
C1—C2—H2	109.0	C7—C8—Br1	119.4 (2)
O1—C3—C2	124.10 (16)	C10—C9—C8	118.3 (3)
O1—C3—C2ⁱ	124.10 (17)	C10—C9—H9	120.8
C2—C3—C2ⁱ	111.8 (3)	C8—C9—H9	120.8
C5—C4—C2	114.4 (3)	C9—C10—C11	121.1 (3)
C5—C4—H4A	108.7	C9—C10—H10	119.5
C2—C4—H4A	108.7	C11—C10—H10	119.4
C5—C4—H4B	108.7	C10—C11—C6	120.7 (3)
C2—C4—H4B	108.7	C10—C11—H11	119.7
H4A—C4—H4B	107.6	C6—C11—H11	119.7
C4ⁱ—C5—C4	113.3 (4)	C1ⁱ—N1—C1	110.1 (3)
C4ⁱ—C5—H5A	108.9	C1ⁱ—N1—H1A	110.7 (13)
C4—C5—H5A	108.9	C1—N1—H1A	110.7 (14)

N1—C1—C2—C3	59.2 (3)	C2—C1—C6—C11	82.1 (3)
C6—C1—C2—C3	−174.5 (2)	C11—C6—C7—C8	−0.8 (4)
N1—C1—C2—C4	−60.1 (3)	C1—C6—C7—C8	175.0 (3)
C6—C1—C2—C4	66.3 (3)	C6—C7—C8—C9	−0.1 (5)
C4—C2—C3—O1	−113.3 (4)	C6—C7—C8—Br1	−179.3 (2)
C1—C2—C3—O1	122.5 (4)	C7—C8—C9—C10	0.8 (5)
C4—C2—C3—C2ⁱ	65.3 (4)	Br1—C8—C9—C10	180.0 (3)
C1—C2—C3—C2ⁱ	−58.9 (4)	C8—C9—C10—C11	−0.5 (6)
C3—C2—C4—C5	−52.8 (3)	C9—C10—C11—C6	−0.4 (6)
C1—C2—C4—C5	66.7 (4)	C7—C6—C11—C10	1.1 (5)
C2—C4—C5—C4ⁱ	43.3 (5)	C1—C6—C11—C10	−175.0 (3)
N1—C1—C6—C7	30.3 (4)	C6—C1—N1—C1ⁱ	173.61 (18)
C2—C1—C6—C7	−93.7 (3)	C2—C1—N1—C1ⁱ	−62.1 (4)
N1—C1—C6—C11	−153.8 (3)

Symmetry code: (i) x, −y+3/2, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1ⁱⁱ	0.87 (5)	2.41 (5)	3.168 (5)	145 (4)
C1—H1···O1ⁱⁱⁱ	0.98	2.54	3.361 (4)	142

Symmetry codes: (ii) x−1, y, z; (iii) x−1/2, −y+3/2, −z+5/2.

Experimental details

Crystal data
Chemical formula	C₂₀H₁₉Br₂NO
M_r	449.18
Crystal system, space group	Orthorhombic, Pnma
Temperature (K)	298
a, b, c (Å)	7.1595 (6), 24.5891 (19), 10.2598 (6)
V (Å³)	1806.2 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	4.49
Crystal size (mm)	0.34 × 0.25 × 0.18

Data collection
Diffractometer	Bruker SMART CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 1999)
T_min, T_max	0.310, 0.498
No. of measured, independent and observed [I > 2σ(I)] reflections	12758, 2286, 1554
R_int	0.035
(sin θ/λ)_max (Å⁻¹)	0.679

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.103, 1.05
No. of reflections	2286
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)	0.84, −0.71

Computer programs: SMART (Bruker, 1999), SAINT (Bruker, 1999), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1ⁱ	0.87 (5)	2.41 (5)	3.168 (5)	145 (4)
C1—H1···O1ⁱⁱ	0.98	2.54	3.361 (4)	142

Symmetry codes: (i) x−1, y, z; (ii) x−1/2, −y+3/2, −z+5/2.

Acknowledgements

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

References

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