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Acta Crystallogr Sect E Struct Rep Online. 2008 December 1; 64(Pt 12): o2417.
Published online 2008 November 22. doi:  10.1107/S1600536808037653
PMCID: PMC2960143

(E)-2-(4-Fluoro­benzyl­idene)cyclo­octanone

Abstract

The title compound, C15H17FO, was prepared directly from the aldol condensation of cyclo­octa­none with 4-fluoro­benz­aldehyde, catalysed by Pd(Ni,Ce) in the presence of trimethyl­silyl chloride. The eight-membered ring adopts a boat-chair conformation.

Related literature

For related structures, see: Huang, Zhu & Pan (2004 [triangle]); Huang, Zhu, Pan & Wan (2004 [triangle]); Zhu & Pan (2004 [triangle]). For general background, see: Amal Raj & Raghathan (2002 [triangle]); Deli et al. (1984 [triangle]).

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Object name is e-64-o2417-scheme1.jpg

Experimental

Crystal data

  • C15H17FO
  • M r = 232.29
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-64-o2417-efi1.jpg
  • a = 12.0310 (2) Å
  • b = 8.6056 (1) Å
  • c = 12.2438 (2) Å
  • V = 1267.65 (3) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.08 mm−1
  • T = 273 (2) K
  • 0.20 × 0.15 × 0.10 mm

Data collection

  • Bruker APEXII CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 2004 [triangle]) T min = 0.983, T max = 0.998
  • 10067 measured reflections
  • 1584 independent reflections
  • 1584 reflections with I > 2σ(I)
  • R int = 0.036

Refinement

  • R[F 2 > 2σ(F 2)] = 0.037
  • wR(F 2) = 0.082
  • S = 1.07
  • 1584 reflections
  • 155 parameters
  • 1 restraint
  • H-atom parameters constrained
  • Δρmax = 0.11 e Å−3
  • Δρmin = −0.11 e Å−3

Data collection: APEX2 (Bruker, 2004 [triangle]); cell refinement: SAINT (Bruker, 2004 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808037653/rk2112sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808037653/rk2112Isup2.hkl

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

Acknowledgments

The authors thank SCNU for financial support.

supplementary crystallographic information

Comment

Arylmethyllidenecycloalkanones are a particularly important class of compounds which are used as precursors for the synthesis bioactive pyrimidine derivatives (Amal Raj & Raghathan, 2002; Deli et al.1984.) The aldol reaction, which is performed in the presence of strong acids, is one of the most useful reactions in organic chemistry. The reaction between cyclooctanone with 4-fluorobenzaldehyde afforded (E)-2-(4-fluorobenzylidene)cyclooctanone, I, (other than (2,8)-di-4-fluorobenzylidenecyclooctanone in excellent yield in the presence of Pd(Ni, Ce)-TMSCl system, where TMSCl is trimethylsilyl chloride, (Fig. 1) (Huang, Zhu & Pan, 2004; Huang, Zhu, Pan & Wan, 2004; Zhu & Pan, 2004). The molecule of I contains one eight-membered ring which adopts a boat-chair conformation and a phenyl ring. The boat-chair conformation is favourable for the cyclooctanone ring of I (Fig. 2). There are no unusual bond lengths and angles in the I. The C5/C7/C8/C15 torsion angle of -3.2 (3)°, to gather with C5/C7/C8/C9 torsion angle of 179.99 (17)°, describes the E-configuration of the molecule about the C7═C8 bond. The C7═C8 bond doesn't conjugate with C9═O1 bond due to the C7/C8/C9/O1 torsion angle has a value of -31.6 (3)° and the length of the double bonds is also normal. Similarly, the C4/C5/C7/C8 torsion angle has a value of -44.6 (3)° and the dihedral angel between the C7═C8–C5 plane with phenyl ring plane, so the C7═C8 bond do not conjugate with the phenyl ring. From the crystal packing of the title compound, the packing of molecule involves van der Waals interactions.

Experimental

A mixture of cyclooctanone (10 mmol), 4-fluorobenzaldehyde (10 mmol), palladium (0.10 mmol), and TMSCl (11 mmol) was refluxed in acetonitrile (12 ml) under 353 K for 5 h. After being cooled to room temperature, the reaction mixture was poured into water, the residue was filtration through a silica pad, and then washed twice with water, dried under vacuum to yield the products I. Single crystal of the I was obtained by slow evaporation from ethanol at room temperature.

Refinement

The H atoms were positioned geometrically and allowed to ride on their parent atoms, with C–H = 0.93 and 0.97 Å, and Uiso(H) = 1.2Ueq(C).

Figures

Fig. 1.
Pd(Ni, Ce)-TMSCl catalyzed synthesis of the title compound.
Fig. 2.
A view of the molecule of (I), with the atomic numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are shown as a small spheres of arbitrary radius.

Crystal data

C15H17FOF000 = 496
Mr = 232.29Dx = 1.217 Mg m3
Orthorhombic, Pna21Mo Kα radiation λ = 0.71073 Å
Hall symbol: P 2c -2nCell parameters from 2166 reflections
a = 12.0310 (2) Åθ = 2.9–22.2º
b = 8.60560 (10) ŵ = 0.08 mm1
c = 12.2438 (2) ÅT = 273 (2) K
V = 1267.65 (3) Å3Block, colourless
Z = 40.20 × 0.15 × 0.10 mm

Data collection

Bruker APEXII CCD diffractometer1584 independent reflections
Radiation source: Fine-focus sealed tube1584 reflections with I > 2σ(I)
Monochromator: GraphiteRint = 0.036
T = 273(2) Kθmax = 27.9º
[var phi] and ω scansθmin = 2.9º
Absorption correction: multi-scan(SADABS; Sheldrick, 2004)h = −15→12
Tmin = 0.983, Tmax = 0.998k = −11→10
10067 measured reflectionsl = −16→13

Refinement

Refinement on F2Hydrogen site location: Geom
Least-squares matrix: FullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.037  w = 1/[σ2(Fo2) + (0.0347P)2 + 0.02P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.082(Δ/σ)max < 0.001
S = 1.07Δρmax = 0.11 e Å3
1584 reflectionsΔρmin = −0.10 e Å3
155 parametersExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
1 restraintExtinction coefficient: 0.011 (2)
Primary atom site location: DirectAbsolute structure: Since the molecule contains only light atoms, the intensities of 946 Friedels pairs were merged.
Secondary atom site location: Difmap

Special details

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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)

xyzUiso*/Ueq
C10.1978 (2)1.3725 (3)0.0997 (2)0.0624 (7)
H10.15491.44280.13920.075*
C20.1992 (2)1.3747 (3)−0.0114 (3)0.0623 (7)
C30.2606 (2)1.2750 (3)−0.0732 (2)0.0592 (6)
H30.26051.2816−0.14900.071*
C40.32327 (19)1.1634 (2)−0.01984 (19)0.0518 (6)
H40.36551.0940−0.06070.062*
C50.32435 (18)1.1529 (2)0.09343 (18)0.0471 (6)
C60.26236 (18)1.2618 (2)0.1518 (2)0.0564 (6)
H60.26451.26010.22770.068*
C70.39214 (17)1.0387 (2)0.15185 (19)0.0495 (5)
H70.43071.07640.21210.059*
C80.40628 (16)0.8869 (2)0.13044 (17)0.0466 (5)
C90.4813 (2)0.8002 (3)0.20544 (19)0.0529 (6)
C100.4617 (2)0.6306 (3)0.2298 (2)0.0654 (7)
H10A0.38490.60520.21330.078*
H10B0.47350.61240.30710.078*
C110.5378 (2)0.5233 (3)0.1644 (2)0.0694 (8)
H11A0.61380.55810.17450.083*
H11B0.53230.41970.19510.083*
C120.5154 (2)0.5126 (3)0.0430 (2)0.0627 (6)
H12A0.43960.47680.03270.075*
H12B0.56430.43450.01220.075*
C130.53068 (18)0.6639 (3)−0.0216 (2)0.0565 (6)
H13A0.57630.73390.02140.068*
H13B0.57150.6403−0.08790.068*
C140.42430 (19)0.7491 (3)−0.05315 (19)0.0586 (6)
H14A0.38200.6829−0.10200.070*
H14B0.44460.8417−0.09370.070*
C150.34864 (16)0.7973 (2)0.0413 (2)0.0534 (5)
H15A0.28860.86040.01250.064*
H15B0.31590.70460.07280.064*
F10.13754 (15)1.48509 (16)−0.06379 (17)0.0991 (5)
O10.56001 (15)0.86558 (19)0.24861 (14)0.0704 (5)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
C10.0563 (14)0.0496 (14)0.081 (2)0.0065 (11)0.0107 (15)−0.0091 (14)
C20.0545 (14)0.0467 (14)0.086 (2)0.0093 (12)−0.0095 (14)0.0034 (13)
C30.0650 (16)0.0544 (13)0.0583 (15)0.0011 (12)−0.0012 (12)0.0033 (13)
C40.0543 (14)0.0440 (12)0.0572 (15)0.0045 (10)0.0064 (12)−0.0006 (11)
C50.0503 (14)0.0413 (12)0.0499 (14)0.0000 (9)0.0058 (12)−0.0013 (10)
C60.0613 (15)0.0497 (12)0.0583 (14)−0.0031 (11)0.0086 (13)−0.0042 (13)
C70.0552 (13)0.0497 (11)0.0437 (12)−0.0012 (10)0.0040 (11)0.0004 (11)
C80.0446 (12)0.0456 (11)0.0494 (14)−0.0003 (9)0.0051 (11)0.0017 (10)
C90.0619 (15)0.0542 (13)0.0426 (13)0.0023 (12)0.0037 (12)0.0032 (11)
C100.0829 (17)0.0545 (14)0.0587 (16)0.0075 (13)0.0069 (14)0.0140 (12)
C110.0798 (19)0.0520 (13)0.077 (2)0.0113 (12)−0.0010 (16)0.0103 (13)
C120.0629 (14)0.0498 (13)0.0754 (17)0.0080 (10)−0.0007 (14)−0.0058 (14)
C130.0572 (13)0.0571 (13)0.0551 (14)0.0038 (10)0.0045 (11)−0.0084 (11)
C140.0651 (15)0.0564 (13)0.0543 (14)−0.0007 (11)−0.0112 (13)−0.0075 (11)
C150.0454 (11)0.0466 (11)0.0682 (14)0.0005 (9)−0.0094 (13)0.0010 (12)
F10.1013 (12)0.0788 (9)0.1173 (13)0.0376 (9)−0.0210 (11)0.0041 (9)
O10.0841 (12)0.0686 (10)0.0583 (11)−0.0009 (9)−0.0200 (10)0.0053 (8)

Geometric parameters (Å, °)

C1—C21.361 (4)C10—C111.527 (3)
C1—C61.385 (3)C10—H10A0.9700
C1—H10.9300C10—H10B0.9700
C2—C31.361 (3)C11—C121.514 (4)
C2—F11.365 (3)C11—H11A0.9700
C3—C41.384 (3)C11—H11B0.9700
C3—H30.9300C12—C131.535 (3)
C4—C51.390 (3)C12—H12A0.9700
C4—H40.9300C12—H12B0.9700
C5—C61.395 (3)C13—C141.524 (3)
C5—C71.464 (3)C13—H13A0.9700
C6—H60.9300C13—H13B0.9700
C7—C81.343 (3)C14—C151.529 (3)
C7—H70.9300C14—H14A0.9700
C8—C91.488 (3)C14—H14B0.9700
C8—C151.506 (3)C15—H15A0.9700
C9—O11.222 (3)C15—H15B0.9700
C9—C101.508 (3)
C2—C1—C6117.6 (2)H10A—C10—H10B107.8
C2—C1—H1121.2C12—C11—C10116.4 (2)
C6—C1—H1121.2C12—C11—H11A108.2
C1—C2—C3123.6 (2)C10—C11—H11A108.2
C1—C2—F1118.1 (3)C12—C11—H11B108.2
C3—C2—F1118.2 (3)C10—C11—H11B108.2
C2—C3—C4118.1 (2)H11A—C11—H11B107.3
C2—C3—H3121.0C11—C12—C13115.7 (2)
C4—C3—H3121.0C11—C12—H12A108.4
C3—C4—C5121.4 (2)C13—C12—H12A108.4
C3—C4—H4119.3C11—C12—H12B108.4
C5—C4—H4119.3C13—C12—H12B108.4
C4—C5—C6117.6 (2)H12A—C12—H12B107.4
C4—C5—C7122.4 (2)C14—C13—C12115.95 (19)
C6—C5—C7119.9 (2)C14—C13—H13A108.3
C1—C6—C5121.7 (3)C12—C13—H13A108.3
C1—C6—H6119.1C14—C13—H13B108.3
C5—C6—H6119.1C12—C13—H13B108.3
C8—C7—C5128.9 (2)H13A—C13—H13B107.4
C8—C7—H7115.5C13—C14—C15116.02 (19)
C5—C7—H7115.5C13—C14—H14A108.3
C7—C8—C9116.4 (2)C15—C14—H14A108.3
C7—C8—C15125.55 (19)C13—C14—H14B108.3
C9—C8—C15118.01 (17)C15—C14—H14B108.3
O1—C9—C8120.40 (19)H14A—C14—H14B107.4
O1—C9—C10118.8 (2)C8—C15—C14114.40 (16)
C8—C9—C10120.8 (2)C8—C15—H15A108.7
C9—C10—C11112.8 (2)C14—C15—H15A108.7
C9—C10—H10A109.0C8—C15—H15B108.7
C11—C10—H10A109.0C14—C15—H15B108.7
C9—C10—H10B109.0H15A—C15—H15B107.6
C11—C10—H10B109.0
C6—C1—C2—C3−0.2 (4)C7—C8—C9—O1−31.5 (3)
C6—C1—C2—F1−178.79 (18)C15—C8—C9—O1151.4 (2)
C1—C2—C3—C41.3 (4)C7—C8—C9—C10148.4 (2)
F1—C2—C3—C4179.8 (2)C15—C8—C9—C10−28.7 (3)
C2—C3—C4—C5−0.2 (4)O1—C9—C10—C11−79.6 (3)
C3—C4—C5—C6−1.8 (4)C8—C9—C10—C11100.6 (3)
C3—C4—C5—C7−178.35 (18)C9—C10—C11—C12−70.2 (3)
C2—C1—C6—C5−1.9 (4)C10—C11—C12—C1363.3 (3)
C4—C5—C6—C12.9 (3)C11—C12—C13—C14−102.8 (3)
C7—C5—C6—C1179.6 (2)C12—C13—C14—C1558.4 (3)
C4—C5—C7—C8−44.6 (4)C7—C8—C15—C14109.4 (2)
C6—C5—C7—C8138.9 (2)C9—C8—C15—C14−73.8 (2)
C5—C7—C8—C9180.0 (2)C13—C14—C15—C851.9 (3)
C5—C7—C8—C15−3.2 (4)

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: RK2112).

References

  • Amal Raj, A. & Raghathan, R. (2002). Synth. Commun.32, 3295-3300.
  • Bruker (2004). APEX2 and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  • Deli, J., Lorand, T., Szabo, D. & Foldesi, A. (1984). Pharmazie, 39, 539–540. [PubMed]
  • Huang, S.-L., Zhu, Y.-L. & Pan, Y.-J. (2004). Acta Cryst. E60, o1000–o1002.
  • Huang, S.-L., Zhu, Y.-L., Pan, Y.-J. & Wan, H.-T. (2004). Acta Cryst. E60, o1504–o1506.
  • Sheldrick, G. M. (2004). SADABS University of Göttingen, Germany.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Zhu, Y. & Pan, Y. (2004). Chem. Lett.33, 668–669.

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