(1S,4S,5S,6R)-6-(4-Bromo-phen-yl)-5-nitro-bicyclo-[2.2.2]octan-2-one.

The title compound, C(14)H(14)BrNO(3), contains a bicyclic ring system with four chiral centers. The absolute structure was established by the Flack method.

Related literature

For the asymmetric Diels-Alder reaction, which in principle allows the formation of four contiguous asymmetric centers, see: Anrendt et al. (2000 ▶); Northrup & MacMillan (2002 ▶); Xu et al. (2007 ▶); Xu et al. (2008 ▶).

Experimental

Crystal data

C14H14BrNO3

M = 324.17

Orthorhombic,

a = 6.4675 (8) Å

b = 10.0007 (13) Å

c = 20.108 (3) Å

V = 1300.6 (3) Å3

Z = 4

Mo Kα radiation

μ = 3.16 mm−1

T = 293 (2) K

0.38 × 0.33 × 0.27 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.758, T max = 1.000 (expected range = 0.325–0.428)

7669 measured reflections

2823 independent reflections

2201 reflections with I > 2σ(I)

R int = 0.057

Refinement

R[F 2 > 2σ(F 2)] = 0.038

wR(F 2) = 0.084

S = 0.90

2823 reflections

173 parameters

H-atom parameters constrained

Δρmax = 0.63 e Å−3

Δρmin = −0.53 e Å−3

Absolute structure: Flack (1983 ▶), 1161 Friedel pairs

Flack parameter: 0.024 (12)

Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT (Bruker, 2000 ▶); 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.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809001275/pv2129sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809001275/pv2129Isup2.hkl

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

C14H14BrNO3	F(000) = 656
Mr = 324.17	Dx = 1.656 Mg m−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 2565 reflections
a = 6.4675 (8) Å	θ = 4.6–48.7°
b = 10.0007 (13) Å	µ = 3.16 mm−1
c = 20.108 (3) Å	T = 293 K
V = 1300.6 (3) Å3	Prismatic, colorless
Z = 4	0.38 × 0.33 × 0.27 mm

Bruker SMART APEX CCD area-detector diffractometer	2823 independent reflections
Radiation source: fine-focus sealed tube	2201 reflections with I > 2σ(I)
graphite	Rint = 0.057
φ and ω scans	θmax = 27.0°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −8→8
Tmin = 0.758, Tmax = 1.000	k = −12→12
7669 measured reflections	l = −25→18

Refinement on F2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F2 > 2σ(F2)] = 0.038	w = 1/[σ2(Fo2) + (0.043P)2] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.084	(Δ/σ)max = 0.010
S = 0.90	Δρmax = 0.63 e Å−3
2823 reflections	Δρmin = −0.53 e Å−3
173 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
0 restraints	Extinction coefficient: 0.0251 (15)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), 1161 Friedel pairs
Secondary atom site location: difference Fourier map	Flack parameter: 0.024 (12)

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.

	x	y	z	Uiso*/Ueq
Br	0.60615 (7)	0.37916 (4)	0.992203 (17)	0.05507 (17)
N1	0.1712 (5)	0.1860 (3)	0.66087 (18)	0.0450 (8)
O1	0.8682 (4)	0.4856 (3)	0.64840 (13)	0.0589 (8)
O2	0.1115 (4)	0.1257 (3)	0.61231 (14)	0.0583 (7)
O3	0.0748 (5)	0.1934 (4)	0.71214 (16)	0.0764 (10)
C1	0.7048 (6)	0.4361 (4)	0.63535 (17)	0.0390 (9)
C2	0.6837 (6)	0.3111 (4)	0.5941 (2)	0.0446 (10)
H2A	0.7602	0.2389	0.6148	0.054*
H2B	0.7415	0.3264	0.5502	0.054*
C3	0.4587 (5)	0.2721 (4)	0.58773 (18)	0.0381 (9)
H3	0.4457	0.1883	0.5628	0.046*
C4	0.3809 (5)	0.2536 (3)	0.65847 (16)	0.0321 (7)
H4	0.4797	0.1964	0.6821	0.038*
C5	0.3716 (5)	0.3892 (3)	0.69495 (14)	0.0306 (7)
H5	0.2273	0.4190	0.6935	0.037*
C6	0.4991 (6)	0.4916 (4)	0.65427 (17)	0.0353 (8)
H6	0.5158	0.5749	0.6793	0.042*
C7	0.3820 (6)	0.5176 (3)	0.58930 (16)	0.0394 (8)
H7A	0.4634	0.5755	0.5608	0.047*
H7B	0.2523	0.5623	0.5989	0.047*
C8	0.3387 (5)	0.3837 (4)	0.55301 (16)	0.0432 (9)
H8A	0.1918	0.3642	0.5541	0.052*
H8B	0.3815	0.3902	0.5069	0.052*
C9	0.4318 (4)	0.3813 (4)	0.76760 (14)	0.0316 (7)
C10	0.2904 (6)	0.4189 (3)	0.81598 (18)	0.0405 (9)
H10	0.1590	0.4467	0.8033	0.049*
C11	0.3406 (6)	0.4160 (4)	0.88210 (17)	0.0454 (10)
H11	0.2429	0.4391	0.9140	0.054*
C12	0.5348 (5)	0.3790 (4)	0.90080 (15)	0.0384 (8)
C13	0.6804 (6)	0.3425 (3)	0.85488 (17)	0.0374 (9)
H13	0.8123	0.3169	0.8681	0.045*
C14	0.6269 (5)	0.3446 (3)	0.78835 (16)	0.0365 (8)
H14	0.7252	0.3207	0.7567	0.044*

	U11	U22	U33	U12	U13	U23
Br	0.0759 (3)	0.0602 (3)	0.0292 (2)	−0.0056 (2)	−0.00768 (18)	−0.00532 (18)
N1	0.049 (2)	0.0307 (16)	0.055 (2)	−0.0033 (14)	−0.0048 (17)	0.0069 (15)
O1	0.0375 (17)	0.081 (2)	0.0584 (18)	−0.0188 (17)	−0.0023 (14)	0.0023 (15)
O2	0.0513 (15)	0.0495 (16)	0.0741 (18)	−0.0076 (18)	−0.0139 (15)	−0.0171 (16)
O3	0.076 (2)	0.090 (2)	0.062 (2)	−0.040 (2)	0.0159 (18)	0.0028 (18)
C1	0.038 (2)	0.048 (2)	0.031 (2)	−0.0038 (18)	0.0005 (16)	0.0104 (16)
C2	0.041 (2)	0.049 (2)	0.044 (2)	0.0109 (18)	0.0129 (17)	−0.0059 (18)
C3	0.049 (2)	0.033 (2)	0.0330 (19)	0.0027 (17)	−0.0010 (15)	−0.0093 (15)
C4	0.0306 (17)	0.0311 (18)	0.0344 (17)	−0.0006 (17)	−0.0064 (16)	−0.0025 (13)
C5	0.0308 (16)	0.0275 (16)	0.0335 (16)	0.0018 (18)	0.0013 (14)	−0.0029 (15)
C6	0.047 (2)	0.0310 (19)	0.0283 (19)	−0.0028 (18)	−0.0020 (15)	−0.0039 (15)
C7	0.043 (2)	0.0356 (19)	0.0392 (19)	0.0000 (18)	−0.0011 (19)	0.0051 (15)
C8	0.060 (2)	0.0377 (19)	0.0321 (17)	0.002 (2)	−0.0035 (15)	−0.0038 (17)
C9	0.0344 (18)	0.0287 (16)	0.0317 (16)	−0.0055 (18)	0.0025 (12)	−0.0006 (15)
C10	0.0364 (18)	0.047 (2)	0.038 (2)	0.0073 (17)	0.0027 (16)	−0.0044 (16)
C11	0.052 (3)	0.050 (3)	0.034 (2)	0.0054 (18)	0.0104 (17)	−0.0127 (16)
C12	0.053 (2)	0.0354 (19)	0.0268 (16)	−0.0065 (19)	0.0000 (14)	−0.0052 (18)
C13	0.0367 (18)	0.035 (2)	0.041 (2)	−0.0027 (15)	−0.0031 (15)	0.0042 (15)
C14	0.0351 (19)	0.042 (2)	0.0323 (17)	0.0020 (16)	0.0073 (16)	−0.0009 (14)

Br—C12	1.895 (3)	C6—C7	1.532 (5)
N1—O3	1.207 (4)	C6—H6	0.9800
N1—O2	1.211 (4)	C7—C8	1.550 (5)
N1—C4	1.516 (4)	C7—H7A	0.9700
O1—C1	1.196 (4)	C7—H7B	0.9700
C1—C6	1.491 (5)	C8—H8A	0.9700
C1—C2	1.506 (5)	C8—H8B	0.9700
C2—C3	1.512 (5)	C9—C14	1.379 (5)
C2—H2A	0.9700	C9—C10	1.387 (4)
C2—H2B	0.9700	C10—C11	1.369 (5)
C3—C4	1.520 (5)	C10—H10	0.9300
C3—C8	1.529 (5)	C11—C12	1.362 (5)
C3—H3	0.9800	C11—H11	0.9300
C4—C5	1.543 (4)	C12—C13	1.368 (5)
C4—H4	0.9800	C13—C14	1.382 (5)
C5—C9	1.514 (4)	C13—H13	0.9300
C5—C6	1.549 (5)	C14—H14	0.9300
C5—H5	0.9800
O3—N1—O2	123.7 (3)	C1—C6—H6	110.4
O3—N1—C4	117.5 (3)	C7—C6—H6	110.4
O2—N1—C4	118.8 (3)	C5—C6—H6	110.4
O1—C1—C6	125.3 (3)	C6—C7—C8	110.1 (3)
O1—C1—C2	123.0 (4)	C6—C7—H7A	109.6
C6—C1—C2	111.6 (3)	C8—C7—H7A	109.6
C1—C2—C3	110.4 (3)	C6—C7—H7B	109.6
C1—C2—H2A	109.6	C8—C7—H7B	109.6
C3—C2—H2A	109.6	H7A—C7—H7B	108.1
C1—C2—H2B	109.6	C3—C8—C7	108.9 (3)
C3—C2—H2B	109.6	C3—C8—H8A	109.9
H2A—C2—H2B	108.1	C7—C8—H8A	109.9
C2—C3—C4	105.7 (3)	C3—C8—H8B	109.9
C2—C3—C8	109.8 (3)	C7—C8—H8B	109.9
C4—C3—C8	110.4 (3)	H8A—C8—H8B	108.3
C2—C3—H3	110.3	C14—C9—C10	117.6 (3)
C4—C3—H3	110.3	C14—C9—C5	122.8 (3)
C8—C3—H3	110.3	C10—C9—C5	119.6 (3)
N1—C4—C3	112.4 (3)	C11—C10—C9	121.3 (3)
N1—C4—C5	110.0 (3)	C11—C10—H10	119.4
C3—C4—C5	110.5 (3)	C9—C10—H10	119.4
N1—C4—H4	107.9	C12—C11—C10	119.5 (3)
C3—C4—H4	107.9	C12—C11—H11	120.3
C5—C4—H4	107.9	C10—C11—H11	120.3
C9—C5—C4	113.7 (3)	C11—C12—C13	121.4 (3)
C9—C5—C6	114.1 (3)	C11—C12—Br	119.5 (3)
C4—C5—C6	108.0 (3)	C13—C12—Br	119.2 (3)
C9—C5—H5	106.9	C12—C13—C14	118.5 (3)
C4—C5—H5	106.9	C12—C13—H13	120.7
C6—C5—H5	106.9	C14—C13—H13	120.7
C1—C6—C7	106.7 (3)	C9—C14—C13	121.7 (3)
C1—C6—C5	111.3 (3)	C9—C14—H14	119.1
C7—C6—C5	107.4 (3)	C13—C14—H14	119.1
O1—C1—C2—C3	178.7 (4)	C9—C5—C6—C7	−163.8 (3)
C6—C1—C2—C3	−4.0 (4)	C4—C5—C6—C7	68.7 (3)
C1—C2—C3—C4	−58.0 (4)	C1—C6—C7—C8	65.1 (4)
C1—C2—C3—C8	61.1 (4)	C5—C6—C7—C8	−54.4 (4)
O3—N1—C4—C3	−163.6 (3)	C2—C3—C8—C7	−52.1 (4)
O2—N1—C4—C3	17.8 (4)	C4—C3—C8—C7	64.1 (4)
O3—N1—C4—C5	−40.0 (4)	C6—C7—C8—C3	−9.6 (4)
O2—N1—C4—C5	141.4 (3)	C4—C5—C9—C14	63.5 (4)
C2—C3—C4—N1	−167.8 (3)	C6—C5—C9—C14	−61.0 (4)
C8—C3—C4—N1	73.5 (3)	C4—C5—C9—C10	−120.1 (3)
C2—C3—C4—C5	68.9 (3)	C6—C5—C9—C10	115.4 (3)
C8—C3—C4—C5	−49.8 (4)	C14—C9—C10—C11	−1.9 (5)
N1—C4—C5—C9	92.5 (3)	C5—C9—C10—C11	−178.5 (3)
C3—C4—C5—C9	−142.8 (3)	C9—C10—C11—C12	1.8 (6)
N1—C4—C5—C6	−139.8 (3)	C10—C11—C12—C13	−1.0 (6)
C3—C4—C5—C6	−15.1 (4)	C10—C11—C12—Br	178.5 (3)
O1—C1—C6—C7	119.8 (4)	C11—C12—C13—C14	0.4 (6)
C2—C1—C6—C7	−57.4 (4)	Br—C12—C13—C14	−179.1 (3)
O1—C1—C6—C5	−123.4 (4)	C10—C9—C14—C13	1.2 (5)
C2—C1—C6—C5	59.5 (4)	C5—C9—C14—C13	177.7 (3)
C9—C5—C6—C1	79.8 (3)	C12—C13—C14—C9	−0.5 (5)
C4—C5—C6—C1	−47.7 (4)