Acta Cryst. (2008). E64, o2417 [ doi:10.1107/S1600536808037653 ]
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.
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.
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).
Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); 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).
![[Figure 1]](./rk2112fig1thm.gif)
| Fig. 1. Pd(Ni, Ce)-TMSCl catalyzed synthesis of the title compound. |
![[Figure 2]](./rk2112fig2thm.gif)
| 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. |
| C15H17FO | F(000) = 496 |
| Mr = 232.29 | Dx = 1.217 Mg m−3 |
| Orthorhombic, Pna21 | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: P 2c -2n | Cell parameters from 2166 reflections |
| a = 12.0310 (2) Å | θ = 2.9–22.2° |
| b = 8.6056 (1) Å | µ = 0.08 mm−1 |
| c = 12.2438 (2) Å | T = 273 K |
| V = 1267.65 (3) Å3 | Block, colourless |
| Z = 4 | 0.20 × 0.15 × 0.10 mm |
| Bruker APEXII CCD diffractometer | 1584 independent reflections |
| Radiation source: Fine-focus sealed tube | 1584 reflections with I > 2σ(I) |
| Graphite | Rint = 0.036 |
| φ and ω scans | θmax = 27.9°, θmin = 2.9° |
| Absorption correction: multi-scan (SADABS; Sheldrick, 2004) | h = −15→12 |
| Tmin = 0.983, Tmax = 0.998 | k = −11→10 |
| 10067 measured reflections | l = −16→13 |
| Refinement on F2 | Hydrogen site location: Geom |
| Least-squares matrix: Full | H-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 = 1.07 | Δρmax = 0.11 e Å−3 |
| 1584 reflections | Δρmin = −0.10 e Å−3 |
| 155 parameters | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
| 1 restraint | Extinction coefficient: 0.011 (2) |
| Primary atom site location: Direct | Absolute structure: Since the molecule contains only light atoms, the intensities of 946 Friedels pairs were merged. |
| Secondary atom site location: Difmap |
| C15H17FO | V = 1267.65 (3) Å3 |
| Mr = 232.29 | Z = 4 |
| Orthorhombic, Pna21 | Mo Kα radiation |
| a = 12.0310 (2) Å | µ = 0.08 mm−1 |
| b = 8.6056 (1) Å | T = 273 K |
| c = 12.2438 (2) Å | 0.20 × 0.15 × 0.10 mm |
| Bruker APEXII CCD diffractometer | 1584 independent reflections |
| Absorption correction: multi-scan (SADABS; Sheldrick, 2004) | 1584 reflections with I > 2σ(I) |
| Tmin = 0.983, Tmax = 0.998 | Rint = 0.036 |
| 10067 measured reflections | θmax = 27.9° |
| R[F2 > 2σ(F2)] = 0.037 | H-atom parameters constrained |
| wR(F2) = 0.082 | Δρmax = 0.11 e Å−3 |
| S = 1.07 | Δρmin = −0.10 e Å−3 |
| 1584 reflections | Absolute structure: Since the molecule contains only light atoms, the intensities of 946 Friedels pairs were merged. |
| 155 parameters | Flack parameter: ? |
| 1 restraint | Rogers parameter: ? |
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. |
| x | y | z | Uiso*/Ueq | ||
| C1 | 0.1978 (2) | 1.3725 (3) | 0.0997 (2) | 0.0624 (7) | |
| H1 | 0.1549 | 1.4428 | 0.1392 | 0.075* | |
| C2 | 0.1992 (2) | 1.3747 (3) | −0.0114 (3) | 0.0623 (7) | |
| C3 | 0.2606 (2) | 1.2750 (3) | −0.0732 (2) | 0.0592 (6) | |
| H3 | 0.2605 | 1.2816 | −0.1490 | 0.071* | |
| C4 | 0.32327 (19) | 1.1634 (2) | −0.01984 (19) | 0.0518 (6) | |
| H4 | 0.3655 | 1.0940 | −0.0607 | 0.062* | |
| C5 | 0.32435 (18) | 1.1529 (2) | 0.09343 (18) | 0.0471 (6) | |
| C6 | 0.26236 (18) | 1.2618 (2) | 0.1518 (2) | 0.0564 (6) | |
| H6 | 0.2645 | 1.2601 | 0.2277 | 0.068* | |
| C7 | 0.39214 (17) | 1.0387 (2) | 0.15185 (19) | 0.0495 (5) | |
| H7 | 0.4307 | 1.0764 | 0.2121 | 0.059* | |
| C8 | 0.40628 (16) | 0.8869 (2) | 0.13044 (17) | 0.0466 (5) | |
| C9 | 0.4813 (2) | 0.8002 (3) | 0.20544 (19) | 0.0529 (6) | |
| C10 | 0.4617 (2) | 0.6306 (3) | 0.2298 (2) | 0.0654 (7) | |
| H10A | 0.3849 | 0.6052 | 0.2133 | 0.078* | |
| H10B | 0.4735 | 0.6124 | 0.3071 | 0.078* | |
| C11 | 0.5378 (2) | 0.5233 (3) | 0.1644 (2) | 0.0694 (8) | |
| H11A | 0.6138 | 0.5581 | 0.1745 | 0.083* | |
| H11B | 0.5323 | 0.4197 | 0.1951 | 0.083* | |
| C12 | 0.5154 (2) | 0.5126 (3) | 0.0430 (2) | 0.0627 (6) | |
| H12A | 0.4396 | 0.4768 | 0.0327 | 0.075* | |
| H12B | 0.5643 | 0.4345 | 0.0122 | 0.075* | |
| C13 | 0.53068 (18) | 0.6639 (3) | −0.0216 (2) | 0.0565 (6) | |
| H13A | 0.5763 | 0.7339 | 0.0214 | 0.068* | |
| H13B | 0.5715 | 0.6403 | −0.0879 | 0.068* | |
| C14 | 0.42430 (19) | 0.7491 (3) | −0.05315 (19) | 0.0586 (6) | |
| H14A | 0.3820 | 0.6829 | −0.1020 | 0.070* | |
| H14B | 0.4446 | 0.8417 | −0.0937 | 0.070* | |
| C15 | 0.34864 (16) | 0.7973 (2) | 0.0413 (2) | 0.0534 (5) | |
| H15A | 0.2886 | 0.8604 | 0.0125 | 0.064* | |
| H15B | 0.3159 | 0.7046 | 0.0728 | 0.064* | |
| F1 | 0.13754 (15) | 1.48509 (16) | −0.06379 (17) | 0.0991 (5) | |
| O1 | 0.56001 (15) | 0.86558 (19) | 0.24861 (14) | 0.0704 (5) |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| C1 | 0.0563 (14) | 0.0496 (14) | 0.081 (2) | 0.0065 (11) | 0.0107 (15) | −0.0091 (14) |
| C2 | 0.0545 (14) | 0.0467 (14) | 0.086 (2) | 0.0093 (12) | −0.0095 (14) | 0.0034 (13) |
| C3 | 0.0650 (16) | 0.0544 (13) | 0.0583 (15) | 0.0011 (12) | −0.0012 (12) | 0.0033 (13) |
| C4 | 0.0543 (14) | 0.0440 (12) | 0.0572 (15) | 0.0045 (10) | 0.0064 (12) | −0.0006 (11) |
| C5 | 0.0503 (14) | 0.0413 (12) | 0.0499 (14) | 0.0000 (9) | 0.0058 (12) | −0.0013 (10) |
| C6 | 0.0613 (15) | 0.0497 (12) | 0.0583 (14) | −0.0031 (11) | 0.0086 (13) | −0.0042 (13) |
| C7 | 0.0552 (13) | 0.0497 (11) | 0.0437 (12) | −0.0012 (10) | 0.0040 (11) | 0.0004 (11) |
| C8 | 0.0446 (12) | 0.0456 (11) | 0.0494 (14) | −0.0003 (9) | 0.0051 (11) | 0.0017 (10) |
| C9 | 0.0619 (15) | 0.0542 (13) | 0.0426 (13) | 0.0023 (12) | 0.0037 (12) | 0.0032 (11) |
| C10 | 0.0829 (17) | 0.0545 (14) | 0.0587 (16) | 0.0075 (13) | 0.0069 (14) | 0.0140 (12) |
| C11 | 0.0798 (19) | 0.0520 (13) | 0.077 (2) | 0.0113 (12) | −0.0010 (16) | 0.0103 (13) |
| C12 | 0.0629 (14) | 0.0498 (13) | 0.0754 (17) | 0.0080 (10) | −0.0007 (14) | −0.0058 (14) |
| C13 | 0.0572 (13) | 0.0571 (13) | 0.0551 (14) | 0.0038 (10) | 0.0045 (11) | −0.0084 (11) |
| C14 | 0.0651 (15) | 0.0564 (13) | 0.0543 (14) | −0.0007 (11) | −0.0112 (13) | −0.0075 (11) |
| C15 | 0.0454 (11) | 0.0466 (11) | 0.0682 (14) | 0.0005 (9) | −0.0094 (13) | 0.0010 (12) |
| F1 | 0.1013 (12) | 0.0788 (9) | 0.1173 (13) | 0.0376 (9) | −0.0210 (11) | 0.0041 (9) |
| O1 | 0.0841 (12) | 0.0686 (10) | 0.0583 (11) | −0.0009 (9) | −0.0200 (10) | 0.0053 (8) |
| C1—C2 | 1.361 (4) | C10—C11 | 1.527 (3) |
| C1—C6 | 1.385 (3) | C10—H10A | 0.9700 |
| C1—H1 | 0.9300 | C10—H10B | 0.9700 |
| C2—C3 | 1.361 (3) | C11—C12 | 1.514 (4) |
| C2—F1 | 1.365 (3) | C11—H11A | 0.9700 |
| C3—C4 | 1.384 (3) | C11—H11B | 0.9700 |
| C3—H3 | 0.9300 | C12—C13 | 1.535 (3) |
| C4—C5 | 1.390 (3) | C12—H12A | 0.9700 |
| C4—H4 | 0.9300 | C12—H12B | 0.9700 |
| C5—C6 | 1.395 (3) | C13—C14 | 1.524 (3) |
| C5—C7 | 1.464 (3) | C13—H13A | 0.9700 |
| C6—H6 | 0.9300 | C13—H13B | 0.9700 |
| C7—C8 | 1.343 (3) | C14—C15 | 1.529 (3) |
| C7—H7 | 0.9300 | C14—H14A | 0.9700 |
| C8—C9 | 1.488 (3) | C14—H14B | 0.9700 |
| C8—C15 | 1.506 (3) | C15—H15A | 0.9700 |
| C9—O1 | 1.222 (3) | C15—H15B | 0.9700 |
| C9—C10 | 1.508 (3) | ||
| C2—C1—C6 | 117.6 (2) | H10A—C10—H10B | 107.8 |
| C2—C1—H1 | 121.2 | C12—C11—C10 | 116.4 (2) |
| C6—C1—H1 | 121.2 | C12—C11—H11A | 108.2 |
| C1—C2—C3 | 123.6 (2) | C10—C11—H11A | 108.2 |
| C1—C2—F1 | 118.1 (3) | C12—C11—H11B | 108.2 |
| C3—C2—F1 | 118.2 (3) | C10—C11—H11B | 108.2 |
| C2—C3—C4 | 118.1 (2) | H11A—C11—H11B | 107.3 |
| C2—C3—H3 | 121.0 | C11—C12—C13 | 115.7 (2) |
| C4—C3—H3 | 121.0 | C11—C12—H12A | 108.4 |
| C3—C4—C5 | 121.4 (2) | C13—C12—H12A | 108.4 |
| C3—C4—H4 | 119.3 | C11—C12—H12B | 108.4 |
| C5—C4—H4 | 119.3 | C13—C12—H12B | 108.4 |
| C4—C5—C6 | 117.6 (2) | H12A—C12—H12B | 107.4 |
| C4—C5—C7 | 122.4 (2) | C14—C13—C12 | 115.95 (19) |
| C6—C5—C7 | 119.9 (2) | C14—C13—H13A | 108.3 |
| C1—C6—C5 | 121.7 (3) | C12—C13—H13A | 108.3 |
| C1—C6—H6 | 119.1 | C14—C13—H13B | 108.3 |
| C5—C6—H6 | 119.1 | C12—C13—H13B | 108.3 |
| C8—C7—C5 | 128.9 (2) | H13A—C13—H13B | 107.4 |
| C8—C7—H7 | 115.5 | C13—C14—C15 | 116.02 (19) |
| C5—C7—H7 | 115.5 | C13—C14—H14A | 108.3 |
| C7—C8—C9 | 116.4 (2) | C15—C14—H14A | 108.3 |
| C7—C8—C15 | 125.55 (19) | C13—C14—H14B | 108.3 |
| C9—C8—C15 | 118.01 (17) | C15—C14—H14B | 108.3 |
| O1—C9—C8 | 120.40 (19) | H14A—C14—H14B | 107.4 |
| O1—C9—C10 | 118.8 (2) | C8—C15—C14 | 114.40 (16) |
| C8—C9—C10 | 120.8 (2) | C8—C15—H15A | 108.7 |
| C9—C10—C11 | 112.8 (2) | C14—C15—H15A | 108.7 |
| C9—C10—H10A | 109.0 | C8—C15—H15B | 108.7 |
| C11—C10—H10A | 109.0 | C14—C15—H15B | 108.7 |
| C9—C10—H10B | 109.0 | H15A—C15—H15B | 107.6 |
| C11—C10—H10B | 109.0 | ||
| C6—C1—C2—C3 | −0.2 (4) | C7—C8—C9—O1 | −31.5 (3) |
| C6—C1—C2—F1 | −178.79 (18) | C15—C8—C9—O1 | 151.4 (2) |
| C1—C2—C3—C4 | 1.3 (4) | C7—C8—C9—C10 | 148.4 (2) |
| F1—C2—C3—C4 | 179.8 (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—C11 | 100.6 (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—C13 | 63.3 (3) |
| C4—C5—C6—C1 | 2.9 (3) | C11—C12—C13—C14 | −102.8 (3) |
| C7—C5—C6—C1 | 179.6 (2) | C12—C13—C14—C15 | 58.4 (3) |
| C4—C5—C7—C8 | −44.6 (4) | C7—C8—C15—C14 | 109.4 (2) |
| C6—C5—C7—C8 | 138.9 (2) | C9—C8—C15—C14 | −73.8 (2) |
| C5—C7—C8—C9 | 180.0 (2) | C13—C14—C15—C8 | 51.9 (3) |
| C5—C7—C8—C15 | −3.2 (4) |
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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.