(S)-2-[(S,Z)-3-Bromo-1-nitro-4-phenyl-but-3-en-2-yl]cyclo-hexa-none.

In the crystal structure of the title compound, C(16)H(18)BrNO(3), the two stereogenic centres both have an S configuration. The cyclo-hexyl ring adopts a chair conformation. In the crystal, mol-ecules are linked by weak N-O⋯Br contacts [O⋯Br = 3.289 (4) Å].

Related literature

For related structures, see: Li et al. (2010 ▶); Chua et al. (2009 ▶). For the asymmetric Michael reaction, which in principle allows for the formation of two contiguous asymmetric centers, see: Zeng & Zhong (2009 ▶); Roca-Lopez et al. (2010 ▶); Tsogoeva (2007 ▶); Sulzer-Mosse & Alexakis (2007 ▶); Mukherjee et al. (2007 ▶).

Experimental

Crystal data

C16H18BrNO3

M = 352.22

Orthorhombic,

a = 8.0091 (3) Å

b = 12.2395 (6) Å

c = 16.3039 (7) Å

V = 1598.23 (12) Å3

Z = 4

Mo Kα radiation

μ = 2.58 mm−1

T = 296 K

0.33 × 0.29 × 0.25 mm

Data collection

Rigaku R-AXIS RAPID/ZJUG diffractometer

Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ▶) T min = 0.428, T max = 0.525

15575 measured reflections

3636 independent reflections

2369 reflections with I > 2σ(I)

R int = 0.051

Refinement

R[F 2 > 2σ(F 2)] = 0.037

wR(F 2) = 0.114

S = 1.00

3636 reflections

191 parameters

H-atom parameters constrained

Δρmax = 0.82 e Å−3

Δρmin = −1.05 e Å−3

Absolute structure: Flack (1983 ▶), 1548 Friedel pairs

Flack parameter: −0.018 (17)

Data collection: PROCESS-AUTO (Rigaku, 2006 ▶); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku, 2007 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811025633/bt5566sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811025633/bt5566Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536811025633/bt5566Isup3.cml

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

C16H18BrNO3	F(000) = 720
Mr = 352.22	Dx = 1.464 Mg m−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 10471 reflections
a = 8.0091 (3) Å	θ = 3.0–27.4°
b = 12.2395 (6) Å	µ = 2.58 mm−1
c = 16.3039 (7) Å	T = 296 K
V = 1598.23 (12) Å3	Chunk, colorless
Z = 4	0.33 × 0.29 × 0.25 mm

Rigaku R-AXIS RAPID/ZJUG diffractometer	3636 independent reflections
Radiation source: rolling anode	2369 reflections with I > 2σ(I)
graphite	Rint = 0.051
Detector resolution: 10.00 pixels mm-1	θmax = 27.4°, θmin = 3.0°
ω scans	h = −10→10
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −15→15
Tmin = 0.428, Tmax = 0.525	l = −20→21
15575 measured reflections

Refinement on F2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F2 > 2σ(F2)] = 0.037	w = 1/[σ2(Fo2) + (0.P)2 + 4.1524P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.114	(Δ/σ)max = 0.001
S = 1.00	Δρmax = 0.82 e Å−3
3636 reflections	Δρmin = −1.05 e Å−3
191 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
0 restraints	Extinction coefficient: 0.0310 (13)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), 1548 Friedel pairs
Secondary atom site location: difference Fourier map	Flack parameter: −0.018 (17)

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
Br1	0.63058 (7)	0.46482 (5)	0.55564 (4)	0.0619 (2)
N1	0.1663 (6)	0.3677 (4)	0.5794 (3)	0.0571 (13)
O2	0.0229 (5)	0.3856 (5)	0.5610 (4)	0.0905 (15)
O1	0.1693 (7)	0.3171 (5)	0.3392 (3)	0.0885 (16)
C11	0.4279 (6)	0.7079 (4)	0.5742 (3)	0.0460 (13)
C2	0.4282 (7)	0.3931 (5)	0.3846 (3)	0.0495 (13)
H2	0.5210	0.3467	0.4025	0.059*
C1	0.3329 (6)	0.4313 (4)	0.4610 (3)	0.0466 (13)
H1	0.2289	0.4650	0.4420	0.056*
C10	0.3654 (7)	0.6156 (4)	0.5251 (3)	0.0462 (12)
H10	0.2658	0.6305	0.4979	0.055*
O3	0.2193 (7)	0.3763 (5)	0.6486 (3)	0.0933 (17)
C15	0.4339 (8)	0.9025 (5)	0.5950 (4)	0.0655 (18)
H15	0.4060	0.9722	0.5771	0.079*
C16	0.3855 (7)	0.8127 (4)	0.5505 (4)	0.0536 (12)
H16	0.3225	0.8227	0.5031	0.064*
C14	0.5235 (8)	0.8893 (6)	0.6660 (4)	0.0655 (18)
H14	0.5559	0.9500	0.6964	0.079*
C3	0.5005 (8)	0.4881 (5)	0.3337 (4)	0.0604 (16)
H3A	0.4103	0.5348	0.3152	0.073*
H3B	0.5743	0.5314	0.3678	0.073*
C9	0.4228 (6)	0.5152 (4)	0.5117 (3)	0.0460 (12)
C7	0.3176 (9)	0.3261 (5)	0.3272 (4)	0.0614 (17)
C12	0.5181 (8)	0.6956 (5)	0.6466 (4)	0.0606 (16)
H12	0.5470	0.6260	0.6647	0.073*
C8	0.2845 (8)	0.3328 (5)	0.5139 (4)	0.0559 (15)
H8A	0.2324	0.2774	0.4799	0.067*
H8B	0.3837	0.3014	0.5386	0.067*
C6	0.4045 (10)	0.2823 (6)	0.2531 (4)	0.078 (2)
H6A	0.3246	0.2449	0.2183	0.093*
H6B	0.4887	0.2298	0.2698	0.093*
C4	0.5965 (9)	0.4456 (6)	0.2599 (4)	0.079 (2)
H4A	0.6393	0.5069	0.2286	0.094*
H4B	0.6911	0.4028	0.2787	0.094*
C13	0.5651 (9)	0.7863 (6)	0.6919 (4)	0.0696 (19)
H13	0.6254	0.7772	0.7402	0.084*
C5	0.4875 (11)	0.3752 (7)	0.2046 (4)	0.089 (3)
H5A	0.5553	0.3445	0.1611	0.107*
H5B	0.4019	0.4204	0.1797	0.107*

	U11	U22	U33	U12	U13	U23
Br1	0.0516 (3)	0.0585 (3)	0.0756 (4)	0.0081 (3)	−0.0139 (3)	−0.0041 (3)
N1	0.055 (3)	0.056 (3)	0.060 (3)	−0.008 (2)	0.007 (2)	0.013 (2)
O2	0.052 (3)	0.117 (4)	0.102 (4)	0.005 (3)	0.001 (3)	0.006 (4)
O1	0.084 (4)	0.101 (4)	0.080 (3)	−0.019 (3)	−0.015 (3)	−0.023 (3)
C11	0.046 (3)	0.047 (3)	0.045 (3)	−0.001 (2)	0.002 (2)	0.000 (2)
C2	0.053 (3)	0.050 (3)	0.046 (3)	0.005 (3)	−0.004 (2)	−0.004 (2)
C1	0.049 (3)	0.040 (3)	0.052 (3)	−0.002 (2)	−0.004 (2)	0.001 (2)
C10	0.044 (3)	0.048 (3)	0.046 (3)	0.002 (3)	−0.002 (3)	−0.002 (2)
O3	0.098 (4)	0.127 (5)	0.055 (3)	0.012 (3)	−0.002 (3)	0.010 (3)
C15	0.064 (4)	0.043 (3)	0.089 (5)	−0.001 (3)	0.006 (3)	−0.010 (3)
C16	0.053 (3)	0.042 (3)	0.066 (3)	0.006 (3)	−0.001 (3)	−0.001 (3)
C14	0.058 (4)	0.060 (4)	0.078 (5)	−0.012 (3)	0.007 (3)	−0.023 (4)
C3	0.064 (4)	0.057 (4)	0.061 (3)	0.000 (3)	0.008 (3)	0.009 (3)
C9	0.046 (3)	0.043 (3)	0.049 (3)	−0.001 (2)	0.000 (2)	0.002 (2)
C7	0.073 (4)	0.057 (4)	0.054 (4)	0.006 (3)	−0.008 (3)	−0.001 (3)
C12	0.076 (4)	0.050 (4)	0.055 (4)	0.006 (3)	−0.009 (3)	−0.008 (3)
C8	0.063 (4)	0.043 (3)	0.061 (4)	−0.003 (3)	0.005 (3)	−0.001 (3)
C6	0.100 (6)	0.073 (5)	0.060 (4)	0.021 (4)	−0.023 (4)	−0.018 (4)
C4	0.093 (5)	0.087 (5)	0.056 (4)	0.003 (5)	0.015 (4)	0.000 (4)
C13	0.082 (5)	0.065 (4)	0.062 (4)	0.000 (4)	−0.012 (3)	−0.018 (3)
C5	0.123 (7)	0.087 (6)	0.057 (4)	0.024 (5)	0.006 (4)	−0.005 (4)

Br1—C9	1.914 (5)	C16—H16	0.9300
N1—O2	1.208 (6)	C14—C13	1.371 (9)
N1—O3	1.209 (6)	C14—H14	0.9300
N1—C8	1.490 (7)	C3—C4	1.520 (8)
O1—C7	1.209 (8)	C3—H3A	0.9700
C11—C16	1.382 (7)	C3—H3B	0.9700
C11—C12	1.393 (8)	C7—C6	1.493 (9)
C11—C10	1.472 (7)	C12—C13	1.385 (8)
C2—C7	1.528 (8)	C12—H12	0.9300
C2—C1	1.535 (7)	C8—H8A	0.9700
C2—C3	1.542 (8)	C8—H8B	0.9700
C2—H2	0.9800	C6—C5	1.536 (9)
C1—C9	1.502 (7)	C6—H6A	0.9700
C1—C8	1.532 (7)	C6—H6B	0.9700
C1—H1	0.9800	C4—C5	1.521 (9)
C10—C9	1.330 (7)	C4—H4A	0.9700
C10—H10	0.9300	C4—H4B	0.9700
C15—C14	1.371 (9)	C13—H13	0.9300
C15—C16	1.373 (8)	C5—H5A	0.9700
C15—H15	0.9300	C5—H5B	0.9700
O2—N1—O3	123.4 (6)	C10—C9—C1	123.8 (5)
O2—N1—C8	118.5 (6)	C10—C9—Br1	122.5 (4)
O3—N1—C8	118.1 (5)	C1—C9—Br1	113.7 (4)
C16—C11—C12	117.7 (5)	O1—C7—C6	123.8 (6)
C16—C11—C10	118.4 (5)	O1—C7—C2	121.3 (6)
C12—C11—C10	123.7 (5)	C6—C7—C2	114.7 (6)
C7—C2—C1	111.9 (5)	C13—C12—C11	120.4 (6)
C7—C2—C3	107.0 (5)	C13—C12—H12	119.8
C1—C2—C3	113.2 (5)	C11—C12—H12	119.8
C7—C2—H2	108.2	N1—C8—C1	109.8 (5)
C1—C2—H2	108.2	N1—C8—H8A	109.7
C3—C2—H2	108.2	C1—C8—H8A	109.7
C9—C1—C8	110.5 (4)	N1—C8—H8B	109.7
C9—C1—C2	114.6 (4)	C1—C8—H8B	109.7
C8—C1—C2	110.0 (4)	H8A—C8—H8B	108.2
C9—C1—H1	107.1	C7—C6—C5	110.6 (6)
C8—C1—H1	107.1	C7—C6—H6A	109.5
C2—C1—H1	107.1	C5—C6—H6A	109.5
C9—C10—C11	132.8 (5)	C7—C6—H6B	109.5
C9—C10—H10	113.6	C5—C6—H6B	109.5
C11—C10—H10	113.6	H6A—C6—H6B	108.1
C14—C15—C16	120.0 (6)	C5—C4—C3	111.8 (6)
C14—C15—H15	120.0	C5—C4—H4A	109.3
C16—C15—H15	120.0	C3—C4—H4A	109.3
C15—C16—C11	121.7 (6)	C5—C4—H4B	109.3
C15—C16—H16	119.2	C3—C4—H4B	109.3
C11—C16—H16	119.2	H4A—C4—H4B	107.9
C15—C14—C13	119.7 (6)	C14—C13—C12	120.5 (6)
C15—C14—H14	120.2	C14—C13—H13	119.8
C13—C14—H14	120.2	C12—C13—H13	119.8
C4—C3—C2	111.0 (5)	C4—C5—C6	111.3 (6)
C4—C3—H3A	109.4	C4—C5—H5A	109.4
C2—C3—H3A	109.4	C6—C5—H5A	109.4
C4—C3—H3B	109.4	C4—C5—H5B	109.4
C2—C3—H3B	109.4	C6—C5—H5B	109.4
H3A—C3—H3B	108.0	H5A—C5—H5B	108.0
C7—C2—C1—C9	−168.6 (5)	C1—C2—C7—O1	7.4 (9)
C3—C2—C1—C9	−47.6 (6)	C3—C2—C7—O1	−117.2 (7)
C7—C2—C1—C8	66.2 (6)	C1—C2—C7—C6	−177.6 (5)
C3—C2—C1—C8	−172.8 (5)	C3—C2—C7—C6	57.8 (7)
C16—C11—C10—C9	152.7 (6)	C16—C11—C12—C13	−1.0 (9)
C12—C11—C10—C9	−31.9 (9)	C10—C11—C12—C13	−176.5 (6)
C14—C15—C16—C11	−1.5 (9)	O2—N1—C8—C1	75.7 (7)
C12—C11—C16—C15	1.8 (9)	O3—N1—C8—C1	−104.4 (6)
C10—C11—C16—C15	177.5 (5)	C9—C1—C8—N1	62.7 (6)
C16—C15—C14—C13	0.4 (10)	C2—C1—C8—N1	−169.7 (5)
C7—C2—C3—C4	−57.4 (7)	O1—C7—C6—C5	119.3 (8)
C1—C2—C3—C4	178.8 (5)	C2—C7—C6—C5	−55.6 (8)
C11—C10—C9—C1	177.3 (5)	C2—C3—C4—C5	58.2 (8)
C11—C10—C9—Br1	−3.0 (9)	C15—C14—C13—C12	0.4 (10)
C8—C1—C9—C10	−116.9 (6)	C11—C12—C13—C14	0.0 (10)
C2—C1—C9—C10	118.1 (6)	C3—C4—C5—C6	−54.1 (8)
C8—C1—C9—Br1	63.3 (5)	C7—C6—C5—C4	51.6 (9)
C2—C1—C9—Br1	−61.7 (5)