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

Zhu, Y.-L.; Xie, M.; Zheng, J.; Deng, C.

doi:10.1107/S1600536808037653

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 64| Part 12| December 2008| Page o2417

doi:10.1107/S1600536808037653

Open

access

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

Yu-Lin Zhu,^a ^* Min Xie,^a Jie Zheng ^a and Changquan Deng ^a

^aSchool of Chemistry and Environment, South China Normal University, Guangzhou 510006, People's Republic of China
^*Correspondence e-mail: yulinzhu2002@yahoo.com.cn

(Received 6 October 2008; accepted 13 November 2008; online 22 November 2008)

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

Experimental

Crystal data

C₁₅H₁₇FO
M_r = 232.29
Orthorhombic, P n a 2₁
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 ) 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[F² > 2σ(F²)] = 0.037
wR(F²) = 0.082
S = 1.07
1584 reflections
155 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.11 e Å⁻³
Δρ_min = −0.11 e Å⁻³

Data collection: APEX2 (Bruker, 2004 ); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT; 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.

Supporting information

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

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

checkCIF report

Comment top

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.

Related literature top

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

Experimental top

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.

Computing details top

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).

Figures top

	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.

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

Crystal data top

C₁₅H₁₇FO	F(000) = 496
M_r = 232.29	D_x = 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

Data collection top

Bruker APEXII CCD diffractometer	1584 independent reflections
Radiation source: Fine-focus sealed tube	1584 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.036
ϕ and ω scans	θ_max = 27.9°, θ_min = 2.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	h = −15→12
T_min = 0.983, T_max = 0.998	k = −11→10
10067 measured reflections	l = −16→13

Refinement top

Refinement on F²	Hydrogen site location: Geom
Least-squares matrix: Full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.037	w = 1/[σ²(F_o²) + (0.0347P)² + 0.02P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.082	(Δ/σ)_max < 0.001
S = 1.07	Δρ_max = 0.11 e Å⁻³
1584 reflections	Δρ_min = −0.11 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

Crystal data top

C₁₅H₁₇FO	V = 1267.65 (3) Å³
M_r = 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

Data collection top

Bruker APEXII CCD diffractometer	1584 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	1584 reflections with I > 2σ(I)
T_min = 0.983, T_max = 0.998	R_int = 0.036
10067 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.037	1 restraint
wR(F²) = 0.082	H-atom parameters constrained
S = 1.07	Δρ_max = 0.11 e Å⁻³
1584 reflections	Δρ_min = −0.11 e Å⁻³
155 parameters	Absolute structure: Since the molecule contains only light atoms, the intensities of 946 Friedels pairs were merged.

Special details top

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) top

	x	y	z	U_iso*/U_eq
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)

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Experimental details

Crystal data
Chemical formula	C₁₅H₁₇FO
M_r	232.29
Crystal system, space group	Orthorhombic, Pna2₁
Temperature (K)	273
a, b, c (Å)	12.0310 (2), 8.6056 (1), 12.2438 (2)
V (Å³)	1267.65 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.20 × 0.15 × 0.10

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2004)
T_min, T_max	0.983, 0.998
No. of measured, independent and observed [I > 2σ(I)] reflections	10067, 1584, 1584
R_int	0.036
(sin θ/λ)_max (Å⁻¹)	0.658

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.082, 1.07
No. of reflections	1584
No. of parameters	155
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.11, −0.11
Absolute structure	Since the molecule contains only light atoms, the intensities of 946 Friedels pairs were merged.

Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Acknowledgements

The authors thank SCNU for financial support.

References

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