2,4-Bis(4-bromo-phen-yl)-3-aza-bicyclo-[3.3.1]nonan-9-one.

The title compound, C(20)H(19)Br(2)NO, shows a chair-chair conformation for the aza-bicycle with an equatorial disposition of the 4-bromo-phenyl groups [dihedral angle between the aromatic rings = 16.48 (3)°]. In the crystal, a short Br⋯Br contact [3.520 (4) Å] occurs and the structure is further stabilized by N-H⋯O hydrogen bonds and C-H⋯O inter-actions.

Related literature

For general background to the biological properties of 3-aza­bicyclo­nona­nes, see: Jeyaraman & Avila (1981 ▶); Hardick et al. (1996 ▶); Barker et al. (2005 ▶). For different conformations for the aza­bicycle, see: Parthiban et al. (2008a ▶,b ▶,c ▶,d ▶, 2009 ▶); Smith-Verdier et al. (1983 ▶); Padegimas & Kovacic (1972 ▶). For ring puckering analysis, see: Cremer & Pople (1975 ▶).

Experimental

Crystal data

C20H19Br2NO

M = 449.18

Triclinic,

a = 6.9415 (3) Å

b = 10.4489 (4) Å

c = 13.2888 (5) Å

α = 101.542 (2)°

β = 100.391 (2)°

γ = 94.472 (2)°

V = 922.34 (6) Å3

Z = 2

Mo Kα radiation

μ = 4.40 mm−1

T = 298 K

0.38 × 0.25 × 0.20 mm

Data collection

Bruker SMART APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker 1999 ▶) T min = 0.280, T max = 0.415

12376 measured reflections

4036 independent reflections

2805 reflections with I > 2σ(I)

R int = 0.024

Refinement

R[F 2 > 2σ(F 2)] = 0.038

wR(F 2) = 0.089

S = 1.02

4036 reflections

221 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.85 e Å−3

Δρmin = −0.92 e Å−3

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

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809017565/hb2967sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809017565/hb2967Isup2.hkl

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

C20H19Br2NO	Z = 2
Mr = 449.18	F(000) = 448
Triclinic, P1	Dx = 1.617 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.9415 (3) Å	Cell parameters from 4458 reflections
b = 10.4489 (4) Å	θ = 2.3–23.7°
c = 13.2888 (5) Å	µ = 4.40 mm−1
α = 101.542 (2)°	T = 298 K
β = 100.391 (2)°	Block, colourless
γ = 94.472 (2)°	0.38 × 0.25 × 0.20 mm
V = 922.34 (6) Å3

Bruker SMART CCD diffractometer	4036 independent reflections
Radiation source: fine-focus sealed tube	2805 reflections with I > 2σ(I)
graphite	Rint = 0.024
φ and ω scans	θmax = 28.3°, θmin = 1.6°
Absorption correction: multi-scan (SADABS; Bruker 1999)	h = −9→9
Tmin = 0.280, Tmax = 0.415	k = −13→10
12376 measured reflections	l = −16→17

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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.089	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ2(Fo2) + (0.0266P)2 + 1.1237P] where P = (Fo2 + 2Fc2)/3
4036 reflections	(Δ/σ)max = 0.001
221 parameters	Δρmax = 0.85 e Å−3
0 restraints	Δρmin = −0.92 e Å−3

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 takeninto account individually in the estimation of e.s.d.'s in distances, anglesand torsion angles; correlations between e.s.d.'s in cell parameters are onlyused 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.

	x	y	z	Uiso*/Ueq
Br1	0.51212 (7)	−0.32865 (4)	0.04459 (3)	0.07124 (16)
Br2	0.76344 (6)	0.92093 (4)	0.40986 (3)	0.06669 (15)
C1	0.2024 (4)	0.1542 (3)	0.2864 (2)	0.0314 (6)
H1	0.1988	0.1411	0.3571	0.038*
C2	−0.0130 (4)	0.1605 (3)	0.2300 (2)	0.0354 (7)
H2	−0.0943	0.0792	0.2291	0.043*
C3	−0.0360 (5)	0.1813 (3)	0.1177 (2)	0.0469 (8)
H3A	0.0242	0.1136	0.0771	0.056*
H3B	−0.1754	0.1706	0.0864	0.056*
C4	0.0554 (5)	0.3150 (4)	0.1097 (3)	0.0539 (9)
H4A	0.1974	0.3158	0.1199	0.065*
H4B	0.0080	0.3287	0.0399	0.065*
C5	0.0073 (5)	0.4269 (3)	0.1896 (3)	0.0492 (8)
H5A	−0.1279	0.4427	0.1669	0.059*
H5B	0.0921	0.5061	0.1915	0.059*
C6	0.0320 (4)	0.4019 (3)	0.3006 (2)	0.0381 (7)
H6	−0.0204	0.4722	0.3446	0.046*
C7	0.2472 (4)	0.3925 (3)	0.3542 (2)	0.0328 (6)
H7	0.2449	0.3782	0.4247	0.039*
C8	−0.0841 (4)	0.2732 (3)	0.2963 (2)	0.0359 (7)
C9	0.2870 (4)	0.0391 (3)	0.2290 (2)	0.0317 (6)
C10	0.4256 (4)	0.0528 (3)	0.1678 (2)	0.0365 (7)
H10	0.4721	0.1363	0.1618	0.044*
C11	0.4958 (4)	−0.0566 (3)	0.1153 (2)	0.0405 (7)
H11	0.5920	−0.0464	0.0761	0.049*
C12	0.4230 (5)	−0.1791 (3)	0.1214 (2)	0.0410 (7)
C13	0.2850 (5)	−0.1960 (3)	0.1810 (3)	0.0509 (9)
H13	0.2359	−0.2800	0.1846	0.061*
C14	0.2202 (5)	−0.0867 (3)	0.2355 (3)	0.0458 (8)
H14	0.1295	−0.0978	0.2776	0.055*
C15	0.3781 (4)	0.5192 (3)	0.3658 (2)	0.0324 (6)
C16	0.3485 (4)	0.6307 (3)	0.4353 (2)	0.0385 (7)
H16	0.2501	0.6248	0.4739	0.046*
C17	0.4611 (4)	0.7499 (3)	0.4489 (2)	0.0427 (7)
H17	0.4379	0.8238	0.4951	0.051*
C18	0.6087 (4)	0.7574 (3)	0.3925 (2)	0.0402 (7)
C19	0.6428 (4)	0.6494 (3)	0.3236 (3)	0.0438 (8)
H19	0.7429	0.6555	0.2862	0.053*
C20	0.5260 (4)	0.5304 (3)	0.3101 (2)	0.0395 (7)
H20	0.5480	0.4572	0.2628	0.047*
N1	0.3217 (3)	0.2793 (2)	0.2964 (2)	0.0328 (5)
O1	−0.2151 (3)	0.2611 (2)	0.34451 (19)	0.0541 (6)
H1A	0.434 (5)	0.275 (3)	0.322 (2)	0.039 (9)*

	U11	U22	U33	U12	U13	U23
Br1	0.1029 (3)	0.0451 (3)	0.0682 (3)	0.0312 (2)	0.0296 (2)	−0.0015 (2)
Br2	0.0736 (3)	0.0415 (2)	0.0772 (3)	−0.01884 (18)	0.0181 (2)	0.0021 (2)
C1	0.0309 (13)	0.0280 (16)	0.0342 (15)	0.0023 (11)	0.0088 (11)	0.0031 (13)
C2	0.0268 (13)	0.0318 (17)	0.0449 (17)	−0.0002 (11)	0.0073 (12)	0.0034 (14)
C3	0.0399 (17)	0.053 (2)	0.0409 (17)	0.0099 (15)	0.0012 (14)	−0.0005 (16)
C4	0.0465 (18)	0.075 (3)	0.0428 (18)	0.0069 (17)	0.0072 (15)	0.0215 (19)
C5	0.0419 (17)	0.042 (2)	0.061 (2)	0.0033 (14)	−0.0021 (15)	0.0169 (18)
C6	0.0304 (14)	0.0334 (18)	0.0474 (17)	0.0084 (12)	0.0075 (13)	−0.0002 (14)
C7	0.0303 (14)	0.0303 (17)	0.0354 (15)	0.0046 (11)	0.0072 (12)	0.0004 (13)
C8	0.0250 (13)	0.0402 (19)	0.0393 (16)	0.0052 (12)	0.0051 (12)	0.0018 (14)
C9	0.0292 (13)	0.0279 (17)	0.0355 (15)	0.0033 (11)	0.0039 (11)	0.0035 (13)
C10	0.0367 (15)	0.0267 (17)	0.0438 (17)	−0.0008 (12)	0.0095 (13)	0.0032 (14)
C11	0.0420 (16)	0.039 (2)	0.0412 (17)	0.0065 (14)	0.0151 (13)	0.0026 (15)
C12	0.0487 (17)	0.0314 (19)	0.0393 (16)	0.0148 (14)	0.0050 (14)	−0.0009 (14)
C13	0.061 (2)	0.0243 (19)	0.069 (2)	0.0026 (15)	0.0199 (18)	0.0094 (17)
C14	0.0490 (18)	0.035 (2)	0.060 (2)	0.0049 (14)	0.0265 (16)	0.0117 (16)
C15	0.0301 (14)	0.0289 (17)	0.0346 (15)	0.0053 (11)	0.0031 (12)	0.0013 (13)
C16	0.0368 (15)	0.0357 (19)	0.0388 (16)	0.0010 (13)	0.0090 (13)	−0.0019 (14)
C17	0.0474 (17)	0.0328 (19)	0.0413 (17)	0.0047 (14)	0.0062 (14)	−0.0048 (14)
C18	0.0405 (16)	0.0307 (18)	0.0441 (17)	−0.0013 (13)	−0.0001 (13)	0.0062 (15)
C19	0.0384 (16)	0.041 (2)	0.0535 (19)	0.0016 (14)	0.0173 (14)	0.0080 (16)
C20	0.0381 (15)	0.0325 (18)	0.0466 (17)	0.0059 (13)	0.0133 (13)	0.0005 (14)
N1	0.0245 (12)	0.0277 (15)	0.0420 (14)	0.0035 (10)	0.0055 (10)	−0.0013 (11)
O1	0.0373 (12)	0.0599 (16)	0.0651 (15)	0.0028 (10)	0.0245 (11)	0.0019 (13)

Br1—C12	1.899 (3)	C7—H7	0.9800
Br2—C18	1.896 (3)	C8—O1	1.216 (3)
C1—N1	1.461 (4)	C9—C10	1.384 (4)
C1—C9	1.510 (4)	C9—C14	1.384 (4)
C1—C2	1.560 (4)	C10—C11	1.386 (4)
C1—H1	0.9800	C10—H10	0.9300
C2—C8	1.497 (4)	C11—C12	1.362 (4)
C2—C3	1.532 (4)	C11—H11	0.9300
C2—H2	0.9800	C12—C13	1.372 (5)
C3—C4	1.519 (5)	C13—C14	1.377 (5)
C3—H3A	0.9700	C13—H13	0.9300
C3—H3B	0.9700	C14—H14	0.9300
C4—C5	1.516 (5)	C15—C20	1.381 (4)
C4—H4A	0.9700	C15—C16	1.388 (4)
C4—H4B	0.9700	C16—C17	1.379 (4)
C5—C6	1.531 (5)	C16—H16	0.9300
C5—H5A	0.9700	C17—C18	1.380 (4)
C5—H5B	0.9700	C17—H17	0.9300
C6—C8	1.498 (4)	C18—C19	1.369 (4)
C6—C7	1.554 (4)	C19—C20	1.392 (4)
C6—H6	0.9800	C19—H19	0.9300
C7—N1	1.461 (4)	C20—H20	0.9300
C7—C15	1.511 (4)	N1—H1A	0.80 (3)
N1—C1—C9	112.3 (2)	O1—C8—C2	123.9 (3)
N1—C1—C2	109.5 (2)	O1—C8—C6	124.0 (3)
C9—C1—C2	110.5 (2)	C2—C8—C6	112.0 (2)
N1—C1—H1	108.1	C10—C9—C14	118.0 (3)
C9—C1—H1	108.1	C10—C9—C1	123.1 (3)
C2—C1—H1	108.1	C14—C9—C1	118.8 (3)
C8—C2—C3	109.2 (3)	C9—C10—C11	120.7 (3)
C8—C2—C1	105.7 (2)	C9—C10—H10	119.7
C3—C2—C1	115.4 (2)	C11—C10—H10	119.7
C8—C2—H2	108.8	C12—C11—C10	119.6 (3)
C3—C2—H2	108.8	C12—C11—H11	120.2
C1—C2—H2	108.8	C10—C11—H11	120.2
C4—C3—C2	114.2 (3)	C11—C12—C13	121.0 (3)
C4—C3—H3A	108.7	C11—C12—Br1	119.4 (2)
C2—C3—H3A	108.7	C13—C12—Br1	119.6 (2)
C4—C3—H3B	108.7	C12—C13—C14	119.0 (3)
C2—C3—H3B	108.7	C12—C13—H13	120.5
H3A—C3—H3B	107.6	C14—C13—H13	120.5
C5—C4—C3	112.7 (3)	C13—C14—C9	121.5 (3)
C5—C4—H4A	109.1	C13—C14—H14	119.2
C3—C4—H4A	109.1	C9—C14—H14	119.2
C5—C4—H4B	109.1	C20—C15—C16	117.9 (3)
C3—C4—H4B	109.1	C20—C15—C7	123.3 (3)
H4A—C4—H4B	107.8	C16—C15—C7	118.8 (2)
C4—C5—C6	114.0 (3)	C17—C16—C15	121.8 (3)
C4—C5—H5A	108.7	C17—C16—H16	119.1
C6—C5—H5A	108.7	C15—C16—H16	119.1
C4—C5—H5B	108.7	C16—C17—C18	118.8 (3)
C6—C5—H5B	108.7	C16—C17—H17	120.6
H5A—C5—H5B	107.6	C18—C17—H17	120.6
C8—C6—C5	108.9 (3)	C19—C18—C17	121.1 (3)
C8—C6—C7	106.3 (2)	C19—C18—Br2	119.8 (2)
C5—C6—C7	115.2 (2)	C17—C18—Br2	119.1 (2)
C8—C6—H6	108.8	C18—C19—C20	119.3 (3)
C5—C6—H6	108.8	C18—C19—H19	120.4
C7—C6—H6	108.8	C20—C19—H19	120.4
N1—C7—C15	112.1 (2)	C15—C20—C19	121.1 (3)
N1—C7—C6	110.0 (2)	C15—C20—H20	119.4
C15—C7—C6	111.1 (2)	C19—C20—H20	119.4
N1—C7—H7	107.8	C1—N1—C7	113.8 (2)
C15—C7—H7	107.8	C1—N1—H1A	110 (2)
C6—C7—H7	107.8	C7—N1—H1A	111 (2)
N1—C1—C2—C8	−58.5 (3)	C1—C9—C10—C11	−178.8 (3)
C9—C1—C2—C8	177.2 (2)	C9—C10—C11—C12	2.1 (5)
N1—C1—C2—C3	62.2 (3)	C10—C11—C12—C13	−1.8 (5)
C9—C1—C2—C3	−62.1 (3)	C10—C11—C12—Br1	177.4 (2)
C8—C2—C3—C4	51.9 (3)	C11—C12—C13—C14	−0.1 (5)
C1—C2—C3—C4	−66.9 (4)	Br1—C12—C13—C14	−179.4 (3)
C2—C3—C4—C5	−45.1 (4)	C12—C13—C14—C9	1.8 (5)
C3—C4—C5—C6	45.8 (4)	C10—C9—C14—C13	−1.5 (5)
C4—C5—C6—C8	−53.2 (3)	C1—C9—C14—C13	176.9 (3)
C4—C5—C6—C7	66.0 (4)	N1—C7—C15—C20	12.5 (4)
C8—C6—C7—N1	56.8 (3)	C6—C7—C15—C20	−111.0 (3)
C5—C6—C7—N1	−63.8 (3)	N1—C7—C15—C16	−167.8 (3)
C8—C6—C7—C15	−178.4 (2)	C6—C7—C15—C16	68.6 (3)
C5—C6—C7—C15	61.0 (3)	C20—C15—C16—C17	0.4 (4)
C3—C2—C8—O1	122.1 (3)	C7—C15—C16—C17	−179.2 (3)
C1—C2—C8—O1	−113.2 (3)	C15—C16—C17—C18	−0.9 (5)
C3—C2—C8—C6	−60.8 (3)	C16—C17—C18—C19	0.6 (5)
C1—C2—C8—C6	63.9 (3)	C16—C17—C18—Br2	179.6 (2)
C5—C6—C8—O1	−121.4 (3)	C17—C18—C19—C20	0.1 (5)
C7—C6—C8—O1	113.9 (3)	Br2—C18—C19—C20	−178.9 (2)
C5—C6—C8—C2	61.4 (3)	C16—C15—C20—C19	0.4 (4)
C7—C6—C8—C2	−63.2 (3)	C7—C15—C20—C19	180.0 (3)
N1—C1—C9—C10	−17.2 (4)	C18—C19—C20—C15	−0.6 (5)
C2—C1—C9—C10	105.4 (3)	C9—C1—N1—C7	−178.3 (2)
N1—C1—C9—C14	164.3 (3)	C2—C1—N1—C7	58.5 (3)
C2—C1—C9—C14	−73.0 (3)	C15—C7—N1—C1	178.2 (2)
C14—C9—C10—C11	−0.4 (4)	C6—C7—N1—C1	−57.6 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1i	0.80 (3)	2.42 (3)	3.191 (3)	162 (3)
C16—H16···O1ii	0.93	2.53	3.242 (3)	133

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O1i	0.80 (3)	2.42 (3)	3.191 (3)	162 (3)
C16—H16⋯O1ii	0.93	2.53	3.242 (3)	133

Symmetry codes: (i) ; (ii) .