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Acta Crystallogr Sect E Struct Rep Online. 2009 August 1; 65(Pt 8): o2012.
Published online 2009 July 29. doi:  10.1107/S1600536809028980
PMCID: PMC2977292

(2R,4R)-2-Hydr­oxy-4-(2-methoxy­phen­yl)bicyclo­[3.3.1]nonan-9-one

Abstract

The title compound, C16H20O3, contains a bicyclic ring system with two chiral centers. The crystal structure is stabilized by inter­molecular O—H(...)O hydrogen bonds. The absolute configuration was established by the stereo-selectivity of the asymmetric organocatalysis.

Related literature

A similar structure is described by Cao et al. (2007 [triangle]). For general background to organocatalysis, see: List et al. (2000 [triangle], 2001 [triangle]); Notz et al. (2001 [triangle]).

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Object name is e-65-o2012-scheme1.jpg

Experimental

Crystal data

  • C16H20O3
  • M r = 260.33
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-65-o2012-efi7.jpg
  • a = 6.9378 (5) Å
  • b = 12.5291 (11) Å
  • c = 16.0726 (14) Å
  • V = 1397.1 (2) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.08 mm−1
  • T = 296 K
  • 0.47 × 0.32 × 0.29 mm

Data collection

  • Rigaku R-AXIS RAPID diffractometer
  • Absorption correction: multi-scan (ABSCOR; Higashi, 1995 [triangle]) T min = 0.945, T max = 0.976
  • 13314 measured reflections
  • 1840 independent reflections
  • 1211 reflections with F 2 > 2σ(F 2)
  • R int = 0.034

Refinement

  • R[F 2 > 2σ(F 2)] = 0.032
  • wR(F 2) = 0.061
  • S = 1.00
  • 1840 reflections
  • 173 parameters
  • H-atom parameters constrained
  • Δρmax = 0.16 e Å−3
  • Δρmin = −0.13 e Å−3

Data collection: PROCESS-AUTO (Rigaku, 2006 [triangle]); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2004 [triangle]), and Larson (1970 [triangle]); program(s) used to solve structure: SIR97 (Altomare et al., 1999 [triangle]); program(s) used to refine structure: CRYSTALS (Watkin et al., 1996 [triangle]); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 [triangle]); software used to prepare material for publication: CrystalStructure (Rigaku/MSC, 2004 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809028980/zl2227sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809028980/zl2227Isup2.hkl

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

Acknowledgments

We acknowledge the help of Professor Jianming Gu of Zhejiang University. We are also grateful for financial support from the Natural Science Foundation of Zhejiang Province Education Department (No. Y200803565).

supplementary crystallographic information

Comment

The natural amino acid L-proline, pioneered by List and Barbas III and their co-workers, has been fully appreciated as an attractive enantioselective organocatalyst for direct asymmetric carbon-carbon and carbon-heteroatom bond-forming reactions, such as aldol (List et al., 2000), Mannich (List et al., 2001) and Michael (Notz et al., 2000) reactions. In our laboratory, a novel tandem Michael-aldol reaction of ketones with cinnamaldehyde derivatives catalyzed by L-proline was developed and a series of new products was obtained. The crystal structure of one of these, the title compound, is reported in this article.

In the crystal structure of the title compound (Fig. 1), both bicyclic six-membered rings display chair conformations in which atoms C1, C8, C4, C3 and atoms C4, C8, C7, C5 each lie in an approximate plane with the dihedral angle between them being 115.9 (0)°. C9 is located above the two planes with similar dihedral angles. The hydroxyl group and the phenyl group are located on different sides of the plane made up of atoms C1, C8, C4, C3. The hydroxyl group is in an axial position, the phenyl group in an equatorial position of the cyclohexanone ring.

Intermolecular O—H···O hydrogen bonds (Tab. 1) connect neighboring molecules with each other to form a one-dimensional chain that stretches along the direction of the a axis (Fig. 2). Via weak C—H···O hydrogen bonds (Tab. 1) molecules are linked along the b axis to form another one-dimensional chain.

Experimental

A DMF (2 ml) solution of cyclohexanone and 3-(2-methoxyphenyl)acryaldehyde in the presence of L-proline as organocatalyst was stirred at room temperature for 48 h. Then the mixture was washed with water (20 ml) and extracted with ethyl acetate (three times). The organic solvent was removed under reduced pressure and the product was purified by silica gel chromatography (pentane: ethyl acetate mixtures). Suitable crystals were obtained by slow evaporation of ethanol at room temperature.

Refinement

In the absence of significant anomalous scatterers Friedel pairs were merged prior to refinement. All H atoms were placed in calculated positions with C—H = 0.98 Å (sp), C—H = 0.97 Å (sp2), C—H= 0.96 Å (sp3), C—H = 0.93 Å (aromatic) and O—H = 0.85 Å and included in the final cycles of refinement in a riding motion approximation, with Uiso(H) = 1.2Ueq of the carrier atoms.

Figures

Fig. 1.
Thermal ellipsoid representation of the of title compound with the atomic labeling scheme. Displacement ellipsoids are drawn at the 40% probability level.
Fig. 2.
View of the hydrogen bonding interactions. H bonds are represented as dashed lines. Symmetery codes: (i) x + 1/2, -y - 1/2, -z. (iv) -x, y + 1/2, 1/2 -z. (v) 1/2 - x, -y - 1, - 1/2 + z.

Crystal data

C16H20O3F(000) = 560.00
Mr = 260.33Dx = 1.238 Mg m3
Orthorhombic, P212121Mo Kα radiation, λ = 0.71075 Å
Hall symbol: P 2ac 2abCell parameters from 8871 reflections
a = 6.9378 (5) Åθ = 3.0–27.4°
b = 12.5291 (11) ŵ = 0.08 mm1
c = 16.0726 (14) ÅT = 296 K
V = 1397.1 (2) Å3Chunk, colorless
Z = 40.47 × 0.32 × 0.29 mm

Data collection

Rigaku R-AXIS RAPID diffractometer1211 reflections with F2 > 2σ(F2)
Detector resolution: 10.00 pixels mm-1Rint = 0.034
ω scansθmax = 27.4°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)h = −8→8
Tmin = 0.945, Tmax = 0.976k = −16→16
13314 measured reflectionsl = −20→20
1840 independent reflections

Refinement

Refinement on F2w = 1/[1.01σ(Fo2)]/(4Fo2)
R[F2 > 2σ(F2)] = 0.032(Δ/σ)max < 0.001
wR(F2) = 0.061Δρmax = 0.16 e Å3
S = 1.00Δρmin = −0.13 e Å3
1840 reflectionsExtinction correction: Larson (1970), equation 22
173 parametersExtinction coefficient: 649 (27)
H-atom parameters constrained

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).

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

xyzUiso*/Ueq
O10.3084 (2)−0.19303 (10)0.07830 (9)0.0638 (4)
O2−0.1217 (2)−0.10943 (12)0.00114 (9)0.0622 (4)
O3−0.10291 (19)0.08144 (11)0.23327 (8)0.0593 (4)
C10.1869 (2)0.03037 (14)0.12399 (11)0.0390 (5)
C20.3817 (2)−0.00912 (14)0.09036 (12)0.0457 (5)
C30.3617 (2)−0.10201 (16)0.02981 (12)0.0476 (5)
C40.2100 (2)−0.08335 (16)−0.03793 (12)0.0472 (5)
C50.2559 (3)0.00623 (18)−0.10098 (12)0.0601 (6)
C60.2481 (3)0.11937 (17)−0.06523 (13)0.0657 (7)
C70.0787 (3)0.13738 (16)−0.00841 (12)0.0599 (6)
C80.0362 (2)0.04651 (14)0.05297 (12)0.0433 (5)
C90.0240 (2)−0.05569 (16)0.00463 (12)0.0440 (5)
C100.1996 (2)0.12898 (14)0.17882 (11)0.0388 (5)
C110.3544 (2)0.19787 (16)0.17853 (12)0.0519 (6)
C120.3625 (3)0.28667 (17)0.23012 (12)0.0653 (7)
C130.2124 (3)0.30819 (18)0.28234 (13)0.0632 (7)
C140.0528 (3)0.24199 (16)0.28470 (12)0.0527 (6)
C150.0475 (2)0.15310 (14)0.23345 (12)0.0437 (5)
C16−0.2463 (2)0.0914 (2)0.29575 (13)0.0707 (7)
H10.1366−0.02700.15930.047*
H30.4868−0.11550.00350.057*
H40.1918−0.1502−0.06870.057*
H8−0.08970.05990.07850.052*
H110.45670.18450.14260.062*
H120.46970.33120.22910.078*
H130.21740.36790.31670.076*
H14−0.04950.25700.32020.063*
H210.4604−0.03200.13690.055*
H220.44480.04950.06190.055*
H510.3847−0.0058−0.12260.072*
H520.16340.0017−0.14610.072*
H610.36550.1322−0.03410.079*
H620.23990.1696−0.11100.079*
H71−0.03480.1477−0.04270.072*
H720.10320.20160.02360.072*
H1010.3263−0.24880.04980.077*
H161−0.32430.02820.29670.085*
H162−0.18560.10070.34890.085*
H163−0.32600.15220.28390.085*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O10.0884 (9)0.0367 (7)0.0664 (9)0.0155 (8)0.0188 (8)0.0031 (7)
O20.0536 (7)0.0633 (10)0.0698 (10)−0.0144 (8)−0.0018 (8)−0.0159 (9)
O30.0580 (7)0.0607 (9)0.0591 (9)−0.0141 (8)0.0173 (7)−0.0219 (7)
C10.0433 (9)0.0327 (10)0.0410 (10)0.0023 (8)0.0029 (8)−0.0021 (8)
C20.0448 (10)0.0422 (11)0.0502 (12)0.0061 (10)−0.0038 (9)−0.0003 (10)
C30.0494 (11)0.0398 (11)0.0537 (12)0.0076 (10)0.0110 (10)−0.0023 (10)
C40.0553 (11)0.0392 (11)0.0472 (11)−0.0009 (10)0.0070 (10)−0.0121 (9)
C50.0638 (13)0.0677 (14)0.0488 (12)0.0024 (13)0.0070 (11)0.0001 (11)
C60.0879 (16)0.0525 (14)0.0566 (14)−0.0027 (14)−0.0052 (13)0.0114 (12)
C70.0857 (15)0.0436 (12)0.0503 (12)0.0147 (12)−0.0154 (12)−0.0024 (11)
C80.0421 (9)0.0428 (11)0.0452 (10)0.0068 (9)−0.0030 (9)−0.0122 (10)
C90.0454 (10)0.0447 (11)0.0420 (11)−0.0015 (10)−0.0025 (9)−0.0042 (10)
C100.0491 (10)0.0333 (10)0.0341 (9)0.0000 (9)−0.0037 (9)−0.0003 (8)
C110.0595 (12)0.0452 (11)0.0509 (12)−0.0091 (11)0.0081 (10)−0.0048 (10)
C120.0772 (14)0.0512 (14)0.0675 (15)−0.0229 (13)0.0124 (13)−0.0159 (12)
C130.0856 (15)0.0440 (13)0.0600 (14)−0.0115 (13)0.0037 (13)−0.0156 (11)
C140.0650 (13)0.0442 (12)0.0488 (12)0.0023 (11)0.0065 (11)−0.0104 (10)
C150.0519 (11)0.0396 (11)0.0397 (11)−0.0022 (9)−0.0024 (10)−0.0023 (10)
C160.0503 (12)0.0801 (17)0.0816 (16)−0.0057 (13)0.0152 (12)−0.0221 (14)

Geometric parameters (Å, °)

O1—C31.430 (2)O1—H1010.846
O2—C91.216 (2)C1—H10.980
O3—C151.376 (2)C2—H210.970
O3—C161.419 (2)C2—H220.970
C1—C21.537 (2)C3—H30.980
C1—C81.561 (2)C4—H40.980
C1—C101.520 (2)C5—H510.970
C2—C31.523 (2)C5—H520.970
C3—C41.533 (2)C6—H610.970
C4—C51.545 (2)C6—H620.970
C4—C91.501 (2)C7—H710.970
C5—C61.531 (3)C7—H720.970
C6—C71.505 (3)C8—H80.980
C7—C81.535 (2)C11—H110.930
C8—C91.500 (2)C12—H120.930
C10—C111.378 (2)C13—H130.930
C10—C151.406 (2)C14—H140.930
C11—C121.389 (2)C16—H1610.960
C12—C131.365 (3)C16—H1620.960
C13—C141.384 (3)C16—H1630.960
C14—C151.386 (2)
C15—O3—C16118.18 (15)O1—C3—H3109.1
C2—C1—C8111.91 (14)C2—C3—H3109.1
C2—C1—C10114.46 (14)C4—C3—H3109.1
C8—C1—C10110.96 (14)C3—C4—H4108.4
C1—C2—C3112.99 (15)C5—C4—H4108.4
O1—C3—C2106.53 (15)C9—C4—H4108.4
O1—C3—C4109.33 (15)C4—C5—H51108.1
C2—C3—C4113.56 (16)C4—C5—H52108.1
C3—C4—C5115.78 (16)C6—C5—H51108.1
C3—C4—C9107.58 (15)C6—C5—H52108.1
C5—C4—C9107.97 (16)H51—C5—H52109.5
C4—C5—C6114.78 (17)C5—C6—H61108.5
C5—C6—C7113.23 (18)C5—C6—H62108.5
C6—C7—C8115.36 (16)C7—C6—H61108.5
C1—C8—C7115.97 (15)C7—C6—H62108.5
C1—C8—C9107.82 (15)H61—C6—H62109.5
C7—C8—C9108.12 (15)C6—C7—H71108.0
O2—C9—C4124.46 (18)C6—C7—H72108.0
O2—C9—C8122.92 (17)C8—C7—H71108.0
C4—C9—C8112.62 (15)C8—C7—H72108.0
C1—C10—C11123.56 (16)H71—C7—H72109.5
C1—C10—C15119.53 (16)C1—C8—H8108.2
C11—C10—C15116.91 (17)C7—C8—H8108.2
C10—C11—C12122.11 (19)C9—C8—H8108.2
C11—C12—C13119.6 (2)C10—C11—H11118.9
C12—C13—C14120.6 (2)C12—C11—H11118.9
C13—C14—C15119.12 (19)C11—C12—H12120.2
O3—C15—C10115.32 (16)C13—C12—H12120.2
O3—C15—C14123.07 (17)C12—C13—H13119.7
C10—C15—C14121.60 (17)C14—C13—H13119.7
C3—O1—H101109.0C13—C14—H14120.4
C2—C1—H1106.3C15—C14—H14120.4
C8—C1—H1106.3O3—C16—H161109.5
C10—C1—H1106.3O3—C16—H162109.5
C1—C2—H21108.6O3—C16—H163109.5
C1—C2—H22108.6H161—C16—H162109.5
C3—C2—H21108.6H161—C16—H163109.5
C3—C2—H22108.6H162—C16—H163109.5
H21—C2—H22109.5
C16—O3—C15—C10170.27 (16)C5—C4—C9—C8−62.1 (2)
C16—O3—C15—C14−8.4 (2)C9—C4—C5—C650.9 (2)
C2—C1—C8—C7−67.5 (2)C4—C5—C6—C7−42.5 (2)
C2—C1—C8—C953.83 (19)C5—C6—C7—C842.9 (2)
C8—C1—C2—C3−47.7 (2)C6—C7—C8—C169.4 (2)
C2—C1—C10—C1119.8 (2)C6—C7—C8—C9−51.8 (2)
C2—C1—C10—C15−160.11 (16)C1—C8—C9—O2116.16 (19)
C10—C1—C2—C3−175.04 (15)C1—C8—C9—C4−63.67 (19)
C8—C1—C10—C11−108.0 (2)C7—C8—C9—O2−117.7 (2)
C8—C1—C10—C1572.1 (2)C7—C8—C9—C462.4 (2)
C10—C1—C8—C761.7 (2)C1—C10—C11—C12−179.26 (18)
C10—C1—C8—C9−176.97 (14)C1—C10—C15—O31.2 (2)
C1—C2—C3—O1−71.93 (19)C1—C10—C15—C14179.90 (17)
C1—C2—C3—C448.5 (2)C11—C10—C15—O3−178.77 (16)
O1—C3—C4—C5−174.64 (15)C11—C10—C15—C14−0.0 (2)
O1—C3—C4—C964.54 (19)C15—C10—C11—C120.7 (2)
C2—C3—C4—C566.5 (2)C10—C11—C12—C13−0.9 (3)
C2—C3—C4—C9−54.3 (2)C11—C12—C13—C140.4 (3)
C3—C4—C5—C6−69.7 (2)C12—C13—C14—C150.2 (3)
C3—C4—C9—O2−116.3 (2)C13—C14—C15—O3178.22 (18)
C3—C4—C9—C863.5 (2)C13—C14—C15—C10−0.4 (2)
C5—C4—C9—O2118.0 (2)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O1—H101···O2i0.851.992.8268 (19)171
O1ii—H101ii···O20.851.992.8268 (19)171
C14—H14···O1iii0.932.513.434 (2)176

Symmetry codes: (i) x+1/2, −y−1/2, −z; (ii) x−1/2, −y−1/2, −z; (iii) −x, y+1/2, −z+1/2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: ZL2227).

References

  • 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.
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  • Farrugia, L. J. (1997). J. Appl. Cryst.30, 565.
  • Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan.
  • Larson, A. C. (1970). Crystallographic Computing, edited by F. R. Ahmed, S. R. Hall & C. P. Huber, pp. 291–294. Copenhagen: Munksgaard.
  • List, B., Lerner, R. A. & Barbas, III (2000). J. Am. Chem. Soc.122, 2395–2396.
  • List, B., Pojarliev, P. & Martin, H. J. (2001). Org. Lett.3, 2423–2425. [PubMed]
  • Notz, W., Sakthivel, K., Bui, T., Zhong, G. & Barbas, C. F. III (2001). Tetrahedron Lett.42, 199–201.
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  • Rigaku/MSC (2004). CrystalStructure Rigaku/MSC, The Woodlands, Texas, USA.
  • Watkin, D. J., Prout, C. K., Carruthers, J. R. & Betteridge, P. W. (1996). CRYSTALS Chemical Crystallography Laboratory, Oxford, England.

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