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The title mol­ecule, C20H20O4, lies on an inversion center. The central alkene moiety is not coplanar with the remainder of the mol­ecule, forming a dihedral angle of 61.61 (12)° with the O-CH2-CH2-C plane and a dihedral angle of 58.70 (11)° with the phenyl plane. The central C=C length is 1.326 (2) Å.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803012315/fl6043sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536803012315/fl6043Isup2.hkl
Contains datablock I

CCDC reference: 217458

Key indicators

  • Single-crystal X-ray study
  • T = 100 K
  • Mean [sigma](C-C) = 0.002 Å
  • R factor = 0.042
  • wR factor = 0.113
  • Data-to-parameter ratio = 22.8

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry








Comment top

During an attempted cross metathesis reaction, the title compound, (I), was produced in an interesting side reaction. Such cross metathesis reactions, which tend to be unpredictable, occur between two olefins in the presence of a Ru catalyst known as Hoyveda's catalyst (Garber et al., 2000). In the reaction, an olefin first reacts with the Ru catalyst, and then the highly reactive intermediate reacts with a different olefin. In this case, the second step was reaction of another molecule of the first olefin, but-3-enyl benzoate, to form the title dimer. The crystal structure determination was carried out in order to identify the unexpected product.

The molecule, which lies on a crystallographic inversion center, is illustrated in Fig. 1. The central 3-hexene moiety is nonplanar, with torsion angle C3—C2—C1—C1i [symmetry code: (i) = 1 − x, 1 − y, 1 − z] of −121.21 (14)°, yielding the dihedral angles given in the abstract.

The title compound has been previously reported as an intermediate in the synthesis of the corresponding 3,4-diol (Torneiro & Still, 1997).

Experimental top

To 15 ml tetrahydrofuran were added but-3-enyl benzoate (0.10 g., 0.56 mmol, 1 eq.), and methyl vinyl ketone (0.85 g, 11.2 mmol, 20 eq.). Hoyveda's catalyst (0.018 g, 0.028 mmol, 0.05 eq) (Garber et al., 2000) was added to the flask in 5 ml dichloromethane. The reaction mixture was stirred until complete by TLC. The reaction mixture was purified by column chromatography to obtain the title compound after removal of solvent.

Refinement top

Hydrogen atoms were placed in idealized positions, with C—H bond distances 0.95–0.99 Å, and thereafter treated as riding. Displacement parameters for H were assigned as Uiso = 1.2Ueq of the attached atom.

Computing details top

Data collection: COLLECT (Nonius, 2000); cell refinement: DENZO and SCALEPACK; data reduction: DENZO and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).

Figures top
[Figure 1] Fig. 1. The title compound, showing the atomic numbering scheme, with displacement parameters drawn at the 50% level.
(I) top
Crystal data top
C20H20O4Z = 1
Mr = 324.36F(000) = 172
Triclinic, P1Dx = 1.270 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 6.829 (3) ÅCell parameters from 2385 reflections
b = 7.508 (2) Åθ = 2.5–30.0°
c = 9.460 (4) ŵ = 0.09 mm1
α = 67.424 (17)°T = 100 K
β = 81.663 (15)°Plate, colorless
γ = 71.322 (16)°0.42 × 0.37 × 0.07 mm
V = 424.1 (3) Å3
Data collection top
KappaCCD
diffractometer (with Oxford Cryostream)
1979 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.021
Graphite monochromatorθmax = 30.0°, θmin = 3.1°
ω scans with κ offsetsh = 99
9345 measured reflectionsk = 1010
2480 independent reflectionsl = 1313
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.042Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.113H-atom parameters constrained
S = 1.05 w = 1/[σ2(Fo2) + (0.0517P)2 + 0.0772P]
where P = (Fo2 + 2Fc2)/3
2480 reflections(Δ/σ)max < 0.001
109 parametersΔρmax = 0.30 e Å3
0 restraintsΔρmin = 0.20 e Å3
Crystal data top
C20H20O4γ = 71.322 (16)°
Mr = 324.36V = 424.1 (3) Å3
Triclinic, P1Z = 1
a = 6.829 (3) ÅMo Kα radiation
b = 7.508 (2) ŵ = 0.09 mm1
c = 9.460 (4) ÅT = 100 K
α = 67.424 (17)°0.42 × 0.37 × 0.07 mm
β = 81.663 (15)°
Data collection top
KappaCCD
diffractometer (with Oxford Cryostream)
1979 reflections with I > 2σ(I)
9345 measured reflectionsRint = 0.021
2480 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0420 restraints
wR(F2) = 0.113H-atom parameters constrained
S = 1.05Δρmax = 0.30 e Å3
2480 reflectionsΔρmin = 0.20 e Å3
109 parameters
Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'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
xyzUiso*/Ueq
O10.11730 (10)0.70498 (11)0.12298 (8)0.02549 (17)
O20.22346 (11)0.81072 (11)0.17281 (8)0.02958 (19)
C10.43531 (15)0.47590 (14)0.46947 (11)0.0250 (2)
H10.36890.37970.53610.030*
C20.38650 (15)0.56267 (15)0.30258 (11)0.0253 (2)
H2A0.42990.45360.26030.030*
H2B0.46470.66090.24650.030*
C30.15700 (14)0.66633 (15)0.27988 (11)0.0241 (2)
H3A0.07600.57870.35150.029*
H3B0.11780.79430.29870.029*
C40.08221 (14)0.77226 (14)0.08580 (11)0.0226 (2)
C50.10756 (14)0.79355 (13)0.07446 (11)0.0227 (2)
C60.30669 (15)0.86558 (15)0.13057 (12)0.0263 (2)
H60.42260.89590.06600.032*
C70.33613 (17)0.89324 (15)0.28083 (12)0.0291 (2)
H70.47180.94490.31960.035*
C80.16690 (17)0.84526 (15)0.37391 (12)0.0302 (2)
H80.18690.86390.47650.036*
C90.03194 (17)0.77001 (16)0.31778 (12)0.0297 (2)
H90.14730.73580.38160.036*
C100.06215 (15)0.74486 (15)0.16834 (12)0.0262 (2)
H100.19810.69460.13020.031*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0179 (3)0.0336 (4)0.0233 (3)0.0050 (3)0.0009 (2)0.0104 (3)
O20.0215 (4)0.0377 (4)0.0268 (4)0.0053 (3)0.0022 (3)0.0124 (3)
C10.0202 (4)0.0246 (4)0.0279 (5)0.0047 (3)0.0003 (3)0.0085 (4)
C20.0202 (4)0.0283 (5)0.0269 (5)0.0061 (4)0.0005 (3)0.0101 (4)
C30.0208 (4)0.0276 (5)0.0224 (5)0.0053 (3)0.0011 (3)0.0087 (4)
C40.0183 (4)0.0222 (4)0.0256 (5)0.0054 (3)0.0003 (3)0.0072 (3)
C50.0218 (4)0.0202 (4)0.0247 (5)0.0053 (3)0.0007 (3)0.0071 (3)
C60.0220 (5)0.0257 (5)0.0304 (5)0.0044 (4)0.0013 (4)0.0111 (4)
C70.0277 (5)0.0271 (5)0.0328 (5)0.0053 (4)0.0072 (4)0.0109 (4)
C80.0381 (6)0.0270 (5)0.0262 (5)0.0093 (4)0.0037 (4)0.0094 (4)
C90.0305 (5)0.0300 (5)0.0280 (5)0.0073 (4)0.0037 (4)0.0125 (4)
C100.0226 (5)0.0254 (5)0.0280 (5)0.0048 (4)0.0003 (4)0.0090 (4)
Geometric parameters (Å, º) top
O1—C41.3405 (13)C5—C61.3933 (14)
O1—C31.4479 (13)C5—C101.3946 (14)
O2—C41.2104 (12)C6—C71.3905 (15)
C1—C1i1.326 (2)C6—H60.95
C1—C21.5006 (15)C7—C81.3865 (16)
C1—H10.95C7—H70.95
C2—C31.5153 (15)C8—C91.3901 (16)
C2—H2A0.99C8—H80.95
C2—H2B0.99C9—C101.3898 (15)
C3—H3A0.99C9—H90.95
C3—H3B0.99C10—H100.95
C4—C51.4920 (15)
C4—O1—C3115.89 (7)C6—C5—C10119.82 (10)
C1i—C1—C2124.60 (12)C6—C5—C4118.50 (9)
C1i—C1—H1117.7C10—C5—C4121.68 (9)
C2—C1—H1117.7C7—C6—C5120.16 (9)
C1—C2—C3110.66 (8)C7—C6—H6119.9
C1—C2—H2A109.5C5—C6—H6119.9
C3—C2—H2A109.5C8—C7—C6119.80 (10)
C1—C2—H2B109.5C8—C7—H7120.1
C3—C2—H2B109.5C6—C7—H7120.1
H2A—C2—H2B108.1C7—C8—C9120.31 (10)
O1—C3—C2106.81 (8)C7—C8—H8119.8
O1—C3—H3A110.4C9—C8—H8119.8
C2—C3—H3A110.4C10—C9—C8120.04 (10)
O1—C3—H3B110.4C10—C9—H9120.0
C2—C3—H3B110.4C8—C9—H9120.0
H3A—C3—H3B108.6C9—C10—C5119.85 (10)
O2—C4—O1123.51 (9)C9—C10—H10120.1
O2—C4—C5124.63 (9)C5—C10—H10120.1
O1—C4—C5111.86 (8)
C1i—C1—C2—C3121.21 (14)C10—C5—C6—C71.46 (14)
C4—O1—C3—C2171.48 (8)C4—C5—C6—C7178.05 (8)
C1—C2—C3—O1167.53 (7)C5—C6—C7—C81.24 (15)
C3—O1—C4—O24.11 (14)C6—C7—C8—C90.11 (15)
C3—O1—C4—C5175.94 (7)C7—C8—C9—C100.80 (16)
O2—C4—C5—C61.05 (14)C8—C9—C10—C50.58 (15)
O1—C4—C5—C6178.90 (8)C6—C5—C10—C90.54 (15)
O2—C4—C5—C10179.45 (9)C4—C5—C10—C9178.95 (9)
O1—C4—C5—C100.60 (13)
Symmetry code: (i) x+1, y+1, z+1.

Experimental details

Crystal data
Chemical formulaC20H20O4
Mr324.36
Crystal system, space groupTriclinic, P1
Temperature (K)100
a, b, c (Å)6.829 (3), 7.508 (2), 9.460 (4)
α, β, γ (°)67.424 (17), 81.663 (15), 71.322 (16)
V3)424.1 (3)
Z1
Radiation typeMo Kα
µ (mm1)0.09
Crystal size (mm)0.42 × 0.37 × 0.07
Data collection
DiffractometerKappaCCD
diffractometer (with Oxford Cryostream)
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
9345, 2480, 1979
Rint0.021
(sin θ/λ)max1)0.703
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.042, 0.113, 1.05
No. of reflections2480
No. of parameters109
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.30, 0.20

Computer programs: COLLECT (Nonius, 2000), DENZO and SCALEPACK (Otwinowski & Minor, 1997), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997).

Selected geometric parameters (Å, º) top
O1—C41.3405 (13)O2—C41.2104 (12)
O1—C31.4479 (13)C1—C1i1.326 (2)
C4—O1—C3115.89 (7)C1i—C1—C2124.60 (12)
C1i—C1—C2—C3121.21 (14)C3—O1—C4—C5175.94 (7)
C4—O1—C3—C2171.48 (8)O1—C4—C5—C100.60 (13)
C1—C2—C3—O1167.53 (7)
Symmetry code: (i) x+1, y+1, z+1.
 

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