(1S,4S,5S,6R)-6-(4-Bromo­phen­yl)-5-nitro­bicyclo­[2.2.2]octan-2-one

Xia, A.; Tang, J.; Wang, Y.; Jiang, J.; Luo, S.

doi:10.1107/S1600536809001275

organic compounds

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ISSN: 2056-9890

Volume 65| Part 2| February 2009| Page o326

doi:10.1107/S1600536809001275

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(1S,4S,5S,6R)-6-(4-Bromophenyl)-5-nitrobicyclo[2.2.2]octan-2-one

Aibao Xia,^a Jie Tang,^a Yifeng Wang,^a Junrong Jiang ^a and Shuping Luo ^a ^*

^aState Key Laboratory Breeding Base of Green Chemistry–Synthesis Technology, Zhejiang University of Technology, Hangzhou 310014, People's Republic of China
^*Correspondence e-mail: xiaaibao1983@163.com

(Received 9 December 2008; accepted 11 January 2009; online 17 January 2009)

The title compound, C₁₄H₁₄BrNO₃, 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_r = 324.17
Orthorhombic, P 2₁ 2₁ 2₁
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[F² > 2σ(F²)] = 0.038
wR(F²) = 0.084
S = 0.90
2823 reflections
173 parameters
H-atom parameters constrained
Δρ_max = 0.63 e Å⁻³
Δρ_min = −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.

Supporting information

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

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

checkCIF report

Comment top

There has been growing interest in the study of asymmetric Diels-Alder reaction because it allows in principle the formation of four contiguous asymmetric centers (Anrendt et al., 2000; Northrup & MacMillan, 2002; Xu et al., 2007, 2008). Consequently, we have synthesized a series of Diels-Alder products in our laboratory and the crystal structure and absolute configuration of one of these, the title compound, (I), is reported in this article.

In the title compound (Fig. 1), the nitryl and the 4-bromophenyl groups lie on different sides of the plane defined by C3/C4/C5 atoms with O2—N1—C4—C5 and N1—C4—C5—C9 torsion angles of 141.4 (4) and 92.5 (5)°, respectively. The C5—H5 bond and 4-bromophenyl group are almost coplanar with H5—C5—C9—C10 torsion angle of -2.3°. The structure is devoid of any classical hydrogen bonding and the molecules of (I) are separated by normal van der Waal's forces (Fig. 2).

Related literature top

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 top

A THF (1.0 ml) solution of trans-nitrostyrene (0.75 mmol) and cyclohex-2-enone (1.0 mmol) in the presence of (S)-1-methyl-2-(pyrrolidin-2-ylmethylthio)-1H-imidazole (0.15 mmol) as amine catalyst and benzoic acid (0.15 mmol) as additive at room temperature was subjected to vigorous stirring. After completion of the reaction, the mixture was washed with water (appoximately 300 ml) and extracted with ethyl acetate. The solvent was removed under reduced pressure and the residue was purified by silica gel column chromatography (eluent: petroleum ether-ethoxyethane). Single crystals were obtained by slow evaporation of an ethyl acetate solution.

Computing details top

Data collection: SMART (Bruker, 2001; cell refinement: SAINT (Bruker, 2000); data reduction: SANIT (Bruker, 2000); 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. Molecular structure of the title compound with atomic labeling scheme; displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. Unit cell packing of the title compound.

(1S,4S,5S,6R)-6-(4-Bromophenyl)-5-nitrobicyclo[2.2.2]octan-2-one top

Crystal data top

C₁₄H₁₄BrNO₃	F(000) = 656
M_r = 324.17	D_x = 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

Data collection top

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

Refinement top

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(F_o²) + (0.043P)²] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.084	(Δ/σ)_max = 0.010
S = 0.90	Δρ_max = 0.63 e Å⁻³
2823 reflections	Δρ_min = −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	Absolute structure parameter: 0.024 (12)

Crystal data top

C₁₄H₁₄BrNO₃	V = 1300.6 (3) Å³
M_r = 324.17	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 6.4675 (8) Å	µ = 3.16 mm⁻¹
b = 10.0007 (13) Å	T = 293 K
c = 20.108 (3) Å	0.38 × 0.33 × 0.27 mm

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	2823 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2201 reflections with I > 2σ(I)
T_min = 0.758, T_max = 1.000	R_int = 0.057
7669 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.038	H-atom parameters constrained
wR(F²) = 0.084	Δρ_max = 0.63 e Å⁻³
S = 0.90	Δρ_min = −0.53 e Å⁻³
2823 reflections	Absolute structure: Flack (1983), 1161 Friedel pairs
173 parameters	Absolute structure parameter: 0.024 (12)
0 restraints

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
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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Experimental details

Crystal data
Chemical formula	C₁₄H₁₄BrNO₃
M_r	324.17
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	293
a, b, c (Å)	6.4675 (8), 10.0007 (13), 20.108 (3)
V (Å³)	1300.6 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	3.16
Crystal size (mm)	0.38 × 0.33 × 0.27

Data collection
Diffractometer	Bruker SMART APEX CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.758, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	7669, 2823, 2201
R_int	0.057
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.084, 0.90
No. of reflections	2823
No. of parameters	173
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.63, −0.53
Absolute structure	Flack (1983), 1161 Friedel pairs
Absolute structure parameter	0.024 (12)

Computer programs: SMART (Bruker, 2001, SAINT (Bruker, 2000), SANIT (Bruker, 2000), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Acknowledgements

We acknowledge the help of Professor Jie Sun of Shanghai Institute of Organic Chemistry.

References

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