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Acta Crystallographica Section E: Structure Reports Online logoLink to Acta Crystallographica Section E: Structure Reports Online
. 2009 Jul 29;65(Pt 8):o2023. doi: 10.1107/S1600536809029213

(S)-2-[(S,E)-4-(4-Chloro­phen­yl)-1-nitro­but-3-en-2-yl]cyclo­hexa­none

Zhaobo Li a, Yi Guo a, Bailin Li b, Shuping Luo a,*
PMCID: PMC2977405  PMID: 21583692

Abstract

The title compound, C16H18ClNO3, was obtained by the organocatalytic asymmetric Michael addition of cyclo­hexa­none to 1-chloro-4-[(1E,3E)-4-nitro­buta-1,3-dien­yl]benzene. The double bond has an E configuration. The cyclo­hexa­none ring adopts a chair conformation. The conformation of the mol­ecule is stabilized by a weak intra­molecular C—H⋯O hydrogen bond.

Related literature

For asymmetric Michael addition reactions employing chiral organo­catalysts, see: Belot et al. (2008 ▶); Dalko & Moisan (2004 ▶); Yu et al. (2009 ▶). For details of the synthesis, see: Xu et al. (2008 ▶); For puckering parameters, see: Cremer & Pople (1975 ▶).graphic file with name e-65-o2023-scheme1.jpg

Experimental

Crystal data

  • C16H18ClNO3

  • M r = 307.78

  • Orthorhombic, Inline graphic

  • a = 5.5300 (3) Å

  • b = 8.5175 (6) Å

  • c = 34.0903 (18) Å

  • V = 1605.71 (17) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 0.25 mm−1

  • T = 296 K

  • 0.48 × 0.32 × 0.28 mm

Data collection

  • Rigaku R-AXIS RAPID diffractometer

  • Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ▶) T min = 0.879, T max = 0.933

  • 15644 measured reflections

  • 2148 independent reflections

  • 1391 reflections with F 2 > 2σ(F 2)

  • R int = 0.034

Refinement

  • R[F 2 > 2σ(F 2)] = 0.044

  • wR(F 2) = 0.124

  • S = 1.00

  • 2148 reflections

  • 192 parameters

  • H-atom parameters constrained

  • Δρmax = 0.22 e Å−3

  • Δρmin = −0.27 e Å−3

  • Absolute structure: Flack (1983 ▶), 1486 Friedel pairs

  • Flack parameter: 0.27 (18)

Data collection: PROCESS-AUTO (Rigaku, 2006 ▶); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku, 2007 ▶); program(s) used to solve structure: SIR97 (Altomare et al., 1999 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: CrystalStructure.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809029213/bx2224sup1.cif

e-65-o2023-sup1.cif (17.8KB, cif)

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809029213/bx2224Isup2.hkl

e-65-o2023-Isup2.hkl (105.6KB, hkl)

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A D—H H⋯A D⋯A D—H⋯A
C8—H81⋯O1 0.97 2.37 3.020 (4) 124
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Acknowledgments

We acknowledge the help of Professor Jianming Gu of Zhejiang University. We are also grateful for financial support by the Catalytic Hydrogenation Research Center of Zhejiang University of Technology.

supplementary crystallographic information

Comment

As one of the most important chiral carbon-carbon bond-forming processes in modern organic chemistry, the field of asymmetric Michael addition employing chiral organocatalysts has gained more and more attention and become the focus of intense research efforts (Dalko & Moisan, 2004; Belot et al., 2008; Yu et al., 2009). Consequently, we have synthesized a series of Michael adducts by employing cyclo-ketones to nitrodienes in our laboratory. We report here the crystal structure and the absolute configuration of the title compound, (I). The cyclohexanone ring adopts a chair conformation as shown by the Cremer & Pople (1975) puckering parameters [QT = 0.568 (4) Å , θ=3.9 (4)° , φ=355 (6) °]. The C1—C9—C10—C11 torsion angle of 175.2 (3) confirms the E configuration of the molecule with respect to the C9═C10 bond. The conformation of (I) is stabilized by one weak intramolecular C—H···O hydrogen bond, Table 1, Fig 1.

Experimental

A 1,2-dichloroethane (0.5 ml) solution of cyclohexanone (0.25 mmol) and 1-chloro-4-((1E,3E)-4-nitrobuta-1,3-dienyl)benzene (0.25 mmol) in the presence of (S)-1-methyl-2-(pyrrolidin-2-ylmethylthio)-1H-imidazole (0.025 mmol) as amine catalyst and (R)-2-(3-(3,5-bis(trifluoromethyl)phenyl)thioureido)-2-phenylacetic acid (0.025 mmol) as acid module at room tempreture was stirred vigorously (Xu et al., 2008). After completion of the reaction, the resulted reaction mixture was purified directly by silica gel column chromatography (eluent: petroleum ether-EtOAc). Single crystals were obtained by slow evaporation of an ethanol-dichloromethane solution.

Refinement

All carbon-bonded H atoms were placed in calculated positions with C—H = 0.93 Å (aromatic), C—H = 0.98 Å (sp2), C—H = 0.97 Å (sp3) and refined using a riding model, with Uiso(H)=1.2eq(C).

The absolute configuration of this compound is established from both the diffraction data and the absolute configuration of a similar compound reported in Xu et al. (2008), therein the organocatalyst has the same structure as in the title compound.

Figures

Fig. 1.

Fig. 1.

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The asymmetric unit of the title compound with the atomic labeling scheme; displacement ellipsoids are drawn at the 30% probability level. Dotted lines show hydrogen bonding.

Crystal data

C16H18ClNO3 F(000) = 648.00
Mr = 307.78 Dx = 1.273 Mg m−3
Orthorhombic, P212121 Mo Kα radiation, λ = 0.71075 Å
Hall symbol: P 2ac 2ab Cell parameters from 9533 reflections
a = 5.5300 (3) Å θ = 3.0–27.4°
b = 8.5175 (6) Å µ = 0.25 mm−1
c = 34.0903 (18) Å T = 296 K
V = 1605.71 (17) Å3 Chunk, colourless
Z = 4 0.48 × 0.32 × 0.28 mm
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Data collection

Rigaku R-AXIS RAPID diffractometer 1391 reflections with F2 > 2σ(F2)
Detector resolution: 10.00 pixels mm-1 Rint = 0.034
ω scans θmax = 27.4°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) h = −7→6
Tmin = 0.879, Tmax = 0.933 k = −11→11
15644 measured reflections l = −43→44
2148 independent reflections
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Refinement

Refinement on F2 (Δ/σ)max = 0.001
R[F2 > 2σ(F2)] = 0.044 Δρmax = 0.22 e Å−3
wR(F2) = 0.124 Δρmin = −0.27 e Å−3
S = 1.00 Extinction correction: SHELXL97 (Sheldrick, 2008)
2148 reflections Extinction coefficient: 0.027 (2)
192 parameters Absolute structure: Flack (1983), 1486 Friedel pairs
H-atom parameters constrained Flack parameter: 0.27 (18)
w = 1/[σ2(Fo2) + (0.032P)2 + 1.2P] where P = (Fo2 + 2Fc2)/3
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Special details

Geometry. ENTER SPECIAL DETAILS OF THE MOLECULAR GEOMETRY
Refinement. Refinement using all reflections. The weighted R-factor (wR) and goodness of fit (S) are based on F2. R-factor (gt) are based on F. The threshold expression of F2 > 2.0 σ(F2) is used only for calculating R-factor (gt).
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Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

x y z Uiso*/Ueq
Cl1 0.6163 (3) 0.6280 (2) 1.07164 (3) 0.1211 (6)
O1 0.9458 (5) 0.1436 (3) 0.77121 (8) 0.0735 (8)
O2 1.2699 (5) 0.5169 (4) 0.83637 (10) 0.0841 (9)
O3 0.9882 (6) 0.6855 (3) 0.84395 (12) 0.1019 (12)
N1 1.0607 (6) 0.5581 (4) 0.83299 (10) 0.0633 (8)
C1 0.8554 (6) 0.3047 (4) 0.84336 (9) 0.0497 (8)
C2 0.6749 (6) 0.1873 (4) 0.82559 (9) 0.0486 (7)
C3 0.6291 (9) 0.0456 (4) 0.85244 (10) 0.0705 (12)
C4 0.4412 (9) −0.0647 (5) 0.83580 (12) 0.0801 (13)
C5 0.5077 (9) −0.1218 (5) 0.79532 (12) 0.0764 (12)
C6 0.5632 (7) 0.0143 (4) 0.76796 (10) 0.0643 (10)
C7 0.7474 (7) 0.1200 (4) 0.78612 (10) 0.0532 (8)
C8 0.8838 (7) 0.4463 (4) 0.81622 (10) 0.0562 (9)
C9 0.7707 (7) 0.3624 (4) 0.88279 (9) 0.0552 (8)
C10 0.8919 (7) 0.3590 (4) 0.91561 (10) 0.0601 (9)
C11 0.8194 (7) 0.4250 (4) 0.95375 (10) 0.0596 (9)
C12 0.6144 (9) 0.5173 (5) 0.95838 (12) 0.0754 (12)
C13 0.5508 (9) 0.5783 (5) 0.99460 (12) 0.0809 (13)
C14 0.6932 (9) 0.5491 (5) 1.02636 (12) 0.0754 (12)
C15 0.8973 (10) 0.4591 (6) 1.02286 (12) 0.0837 (14)
C16 0.9577 (8) 0.3972 (5) 0.98675 (11) 0.0726 (12)
H1 1.0127 0.2531 0.8464 0.060*
H2 0.5206 0.2421 0.8221 0.058*
H9 0.6159 0.4048 0.8839 0.066*
H10 1.0415 0.3092 0.9148 0.072*
H12 0.5177 0.5386 0.9367 0.090*
H13 0.4118 0.6389 0.9972 0.097*
H15 0.9943 0.4398 1.0446 0.100*
H16 1.0952 0.3350 0.9846 0.087*
H31 0.7795 −0.0114 0.8558 0.085*
H32 0.5737 0.0833 0.8777 0.085*
H41 0.4259 −0.1546 0.8531 0.096*
H42 0.2875 −0.0101 0.8344 0.096*
H51 0.3737 −0.1816 0.7847 0.092*
H52 0.6493 −0.1886 0.7972 0.092*
H61 0.6255 −0.0263 0.7434 0.077*
H62 0.4162 0.0732 0.7631 0.077*
H81 0.9403 0.4111 0.7908 0.067*
H82 0.7287 0.4981 0.8133 0.067*
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Atomic displacement parameters (Å2)

U11 U22 U33 U12 U13 U23
Cl1 0.1546 (14) 0.1453 (13) 0.0635 (6) −0.0040 (13) 0.0179 (8) −0.0299 (7)
O1 0.0658 (17) 0.0833 (19) 0.0716 (16) −0.0074 (17) 0.0162 (14) −0.0129 (15)
O2 0.0494 (16) 0.086 (2) 0.117 (2) −0.0064 (16) −0.0101 (17) 0.006 (2)
O3 0.087 (2) 0.0605 (17) 0.158 (3) −0.005 (2) −0.018 (2) −0.023 (2)
N1 0.0585 (19) 0.0535 (18) 0.078 (2) −0.0089 (18) −0.0045 (18) 0.0029 (17)
C1 0.0521 (19) 0.0498 (18) 0.0472 (16) −0.0037 (18) −0.0020 (16) −0.0009 (15)
C2 0.0516 (18) 0.0480 (18) 0.0462 (15) −0.0035 (17) 0.0013 (15) −0.0015 (14)
C3 0.101 (3) 0.061 (2) 0.0486 (18) −0.032 (2) 0.001 (2) 0.0005 (17)
C4 0.109 (3) 0.067 (2) 0.064 (2) −0.037 (2) 0.000 (2) −0.003 (2)
C5 0.095 (3) 0.058 (2) 0.076 (2) −0.010 (2) −0.009 (2) −0.009 (2)
C6 0.072 (2) 0.068 (2) 0.0534 (19) −0.009 (2) −0.0023 (19) −0.0126 (18)
C7 0.057 (2) 0.053 (2) 0.0501 (17) 0.0003 (19) −0.0022 (17) −0.0014 (16)
C8 0.060 (2) 0.050 (2) 0.0583 (19) −0.014 (2) −0.0097 (18) 0.0038 (16)
C9 0.058 (2) 0.055 (2) 0.0526 (17) −0.0046 (19) −0.0029 (17) −0.0023 (17)
C10 0.063 (2) 0.064 (2) 0.0537 (18) 0.005 (2) −0.0053 (18) −0.0025 (17)
C11 0.064 (2) 0.060 (2) 0.0547 (19) −0.005 (2) −0.0032 (18) −0.0040 (17)
C12 0.079 (2) 0.089 (3) 0.058 (2) 0.010 (2) −0.006 (2) −0.006 (2)
C13 0.085 (3) 0.089 (3) 0.069 (2) 0.014 (3) 0.002 (2) −0.012 (2)
C14 0.090 (3) 0.079 (2) 0.058 (2) −0.012 (3) 0.006 (2) −0.007 (2)
C15 0.097 (3) 0.101 (3) 0.053 (2) −0.006 (3) −0.011 (2) −0.005 (2)
C16 0.075 (2) 0.085 (3) 0.059 (2) 0.004 (2) −0.011 (2) −0.003 (2)
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Geometric parameters (Å, °)

Cl1—C14 1.736 (4) C14—C15 1.370 (7)
O1—C7 1.226 (4) C15—C16 1.380 (5)
O2—N1 1.214 (4) C1—H1 0.980
O3—N1 1.216 (4) C2—H2 0.980
N1—C8 1.480 (5) C3—H31 0.970
C1—C2 1.537 (4) C3—H32 0.970
C1—C8 1.528 (4) C4—H41 0.970
C1—C9 1.506 (4) C4—H42 0.970
C2—C3 1.536 (5) C5—H51 0.970
C2—C7 1.516 (4) C5—H52 0.970
C3—C4 1.512 (6) C6—H61 0.970
C4—C5 1.509 (5) C6—H62 0.970
C5—C6 1.519 (5) C8—H81 0.970
C6—C7 1.494 (5) C8—H82 0.970
C9—C10 1.305 (4) C9—H9 0.930
C10—C11 1.472 (5) C10—H10 0.930
C11—C12 1.389 (6) C12—H12 0.930
C11—C16 1.381 (5) C13—H13 0.930
C12—C13 1.385 (6) C15—H15 0.930
C13—C14 1.362 (6) C16—H16 0.930
O2—N1—O3 122.9 (3) C2—C3—H32 108.8
O2—N1—C8 118.7 (3) C4—C3—H31 108.8
O3—N1—C8 118.4 (3) C4—C3—H32 108.8
C2—C1—C8 110.0 (2) H31—C3—H32 109.5
C2—C1—C9 111.2 (2) C3—C4—H41 108.8
C8—C1—C9 108.3 (2) C3—C4—H42 108.8
C1—C2—C3 112.5 (2) C5—C4—H41 108.8
C1—C2—C7 115.1 (2) C5—C4—H42 108.8
C3—C2—C7 106.0 (2) H41—C4—H42 109.5
C2—C3—C4 112.2 (3) C4—C5—H51 109.0
C3—C4—C5 112.1 (3) C4—C5—H52 109.0
C4—C5—C6 111.4 (3) C6—C5—H51 109.0
C5—C6—C7 110.1 (3) C6—C5—H52 109.0
O1—C7—C2 122.9 (3) H51—C5—H52 109.5
O1—C7—C6 122.5 (3) C5—C6—H61 109.3
C2—C7—C6 114.5 (3) C5—C6—H62 109.3
N1—C8—C1 110.0 (2) C7—C6—H61 109.3
C1—C9—C10 126.8 (3) C7—C6—H62 109.3
C9—C10—C11 127.5 (3) H61—C6—H62 109.5
C10—C11—C12 122.6 (3) N1—C8—H81 109.3
C10—C11—C16 120.2 (3) N1—C8—H82 109.3
C12—C11—C16 117.2 (3) C1—C8—H81 109.3
C11—C12—C13 121.4 (4) C1—C8—H82 109.3
C12—C13—C14 119.6 (4) H81—C8—H82 109.5
Cl1—C14—C13 119.6 (3) C1—C9—H9 116.6
Cl1—C14—C15 119.7 (3) C10—C9—H9 116.6
C13—C14—C15 120.6 (4) C9—C10—H10 116.2
C14—C15—C16 119.4 (4) C11—C10—H10 116.2
C11—C16—C15 121.8 (4) C11—C12—H12 119.3
C2—C1—H1 109.1 C13—C12—H12 119.3
C8—C1—H1 109.1 C12—C13—H13 120.2
C9—C1—H1 109.1 C14—C13—H13 120.2
C1—C2—H2 107.6 C14—C15—H15 120.3
C3—C2—H2 107.6 C16—C15—H15 120.3
C7—C2—H2 107.6 C11—C16—H16 119.1
C2—C3—H31 108.8 C15—C16—H16 119.1
O2—N1—C8—C1 64.7 (4) C3—C4—C5—C6 −52.9 (5)
O3—N1—C8—C1 −112.9 (3) C4—C5—C6—C7 52.5 (5)
C2—C1—C8—N1 −179.0 (2) C5—C6—C7—O1 118.3 (4)
C8—C1—C2—C3 −177.3 (3) C5—C6—C7—C2 −58.0 (4)
C8—C1—C2—C7 61.1 (3) C1—C9—C10—C11 175.2 (3)
C2—C1—C9—C10 126.2 (4) C9—C10—C11—C12 −7.3 (6)
C9—C1—C2—C3 −57.3 (4) C9—C10—C11—C16 173.2 (4)
C9—C1—C2—C7 −178.8 (2) C10—C11—C12—C13 −179.8 (4)
C8—C1—C9—C10 −112.8 (4) C10—C11—C16—C15 179.0 (4)
C9—C1—C8—N1 59.2 (3) C12—C11—C16—C15 −0.6 (6)
C1—C2—C3—C4 176.8 (3) C16—C11—C12—C13 −0.2 (6)
C1—C2—C7—O1 7.5 (5) C11—C12—C13—C14 0.8 (7)
C1—C2—C7—C6 −176.2 (3) C12—C13—C14—Cl1 179.0 (3)
C3—C2—C7—O1 −117.6 (4) C12—C13—C14—C15 −0.5 (7)
C3—C2—C7—C6 58.7 (4) Cl1—C14—C15—C16 −179.8 (3)
C7—C2—C3—C4 −56.6 (4) C13—C14—C15—C16 −0.3 (6)
C2—C3—C4—C5 56.4 (4) C14—C15—C16—C11 0.8 (7)
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Hydrogen-bond geometry (Å, °)

D—H···A D—H H···A D···A D—H···A
C8—H81···O1 0.97 2.37 3.020 (4) 124
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Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: BX2224).

References

  1. Altomare, A., Burla, M. C., Camalli, M., Cascarano, G. L., Giacovazzo, C., Guagliardi, A., Moliterni, A. G. G., Polidori, G. & Spagna, R. (1999). J. Appl. Cryst.32, 115–119.
  2. Belot, S., Massaro, A., Tenti, A., Mordini, A. & Alexakis, A. (2008). Org. Lett.10, 4557–4560. [DOI] [PubMed]
  3. Cremer, D. & Pople, J. A. (1975). J. Am. Chem. Soc.97, 1354–1358.
  4. Dalko, P. I. & Moisan, L. (2004). Angew. Chem. Int. Ed.43, 5138–5175. [DOI] [PubMed]
  5. Farrugia, L. J. (1997). J. Appl. Cryst.30, 565.
  6. Flack, H. D. (1983). Acta Cryst. A39, 876–881.
  7. Higashi, T. (1995). ABSCOR Rigaku Corporation, Tokyo, Japan.
  8. Rigaku (2006). PROCESS-AUTO Rigaku Corporation, Tokyo, Japan.
  9. Rigaku (2007). CrystalStructure Rigaku Americas, The Woodlands, Texas, USA.
  10. Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [DOI] [PubMed]
  11. Xu, D., Yue, H., Luo, S., Xia, A., Zhang, S. & Xu, Z. (2008). Org. Biomol. Chem.6, 2054–2057. [DOI] [PubMed]
  12. Yu, Z., Liu, X., Zhou, L., Lin, L. & Feng, X. (2009). Angew. Chem. Int. Ed.48, 5195–5198. [DOI] [PubMed]

Associated Data

This section collects any data citations, data availability statements, or supplementary materials included in this article.

Supplementary Materials

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809029213/bx2224sup1.cif

e-65-o2023-sup1.cif (17.8KB, cif)

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809029213/bx2224Isup2.hkl

e-65-o2023-Isup2.hkl (105.6KB, hkl)

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

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography

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