organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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(E)-2-Meth­­oxy-4-(3-oxobut-1-en­yl)phenyl acetate

aDepartment of Chemistry and Biology, Xiangfan University, Xiangfan 441053, People's Republic of China
*Correspondence e-mail: cch510@126.com

(Received 23 June 2008; accepted 10 July 2008; online 16 July 2008)

The title compound, C13H14O4, belongs to the class of α,β-unsaturated ketones, which have potential bactericidal, fungicidal, anti­tumor and anti-inflammatory properties. The C atoms and attached H atoms of the ethenyl part of the title mol­ecule are disordered over two orientations with refined occupancies of 0.583 (7) and 0.417 (3). Mol­ecules are connected by two inter­molecular C—H⋯O inter­actions, forming a dimer with [\overline{1}] symmetry.

Related literature

For related literature, see: Steiner et al. (1998[Steiner, T. & Desiraju, G. R. (1998). Chem. Commun. pp. 891-892.]); Kuo et al. (2005[Kuo, P.-C., Damu, A. G., Cherng, C.-Y., Jeng, J.-F., Teng, C.-M., Lee, E.-J. & Wu, T.-S. (2005). Arch. Pharm. Res. 28, 518-528.]); Buszek et al. (2007[Buszek, K. R. & Brown, N. (2007). Org. Lett. 9, 707-710.]); Yarishkin et al. (2008[Yarishkin, O. V., Ryu, H. W., Park, J.-Y., Yang, M. S., Hong, S.-G. & Park, K. H. (2008). Bioorg. Med. Chem. Lett. 18, 137-140.]); Etter et al. (1990[Etter, M. C., MacDonald, J. C. & Bernstein, J. (1990). Acta Cryst. B46, 256-262.]).

[Scheme 1]

Experimental

Crystal data
  • C13H14O4

  • Mr = 234.24

  • Triclinic, [P \overline 1]

  • a = 6.2534 (5) Å

  • b = 7.5797 (5) Å

  • c = 13.9718 (8) Å

  • α = 96.611 (2)°

  • β = 91.487 (2)°

  • γ = 110.599 (2)°

  • V = 614.21 (7) Å3

  • Z = 2

  • Mo Kα radiation

  • μ = 0.09 mm−1

  • T = 299 (2) K

  • 0.30 × 0.23 × 0.20 mm

Data collection
  • Bruker SMART 4K CCD area-detector diffractometer

  • Absorption correction: multi-scan (SADABS; Sheldrick, 1997[Sheldrick, G. M. (1997). SADABS. University of Göttingen, Germany.]) Tmin = 0.981, Tmax = 0.989

  • 3984 measured reflections

  • 2381 independent reflections

  • 1423 reflections with I > 2σ(I)

  • Rint = 0.049

Refinement
  • R[F2 > 2σ(F2)] = 0.066

  • wR(F2) = 0.220

  • S = 1.10

  • 2381 reflections

  • 173 parameters

  • 14 restraints

  • H-atom parameters constrained

  • Δρmax = 0.23 e Å−3

  • Δρmin = −0.47 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
C2—H2⋯O1i 0.93 2.58 3.507 (4) 172
Symmetry code: (i) -x+1, -y+1, -z+1.

Data collection: SMART (Bruker, 1997[Bruker (1997). SMART. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 1999[Bruker (1999). SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); software used to prepare material for publication: SHELXTL.

Supporting information


Comment top

The title compound belongs to α,β-unsaturated ketones having potential bactericidal, fungicidal, antitumor and antiinflammatory properties (Kuo et al., 2005; Yarishkin et al., 2008). Sythesis of α,β-unsaturated ketones is being extensively investigated (Buszek et al., 2007). The molecular structure is shown in Fig. 1. The molecules form dimers by a pair of intermolecular C—H···O hydrogen bonds (Steiner et al., 1998) forming a graph-set R22(14) (Etter et al., 1990).

Related literature top

For related literature, see: Steiner et al. (1998); Kuo et al. (2005); Buszek et al. (2007); Yarishkin et al. (2008); Etter et al. (1990).

Experimental top

(E)-4-(4-Hydroxy-3-methoxyphenyl)but-3-en-2-one (1.92 g, 0.01 mol) and Et3N (1.21 g, 0.012 mol) was dissolved in dry CH2Cl2 (50 ml). Acetyl chloride (1.02 g, 0.012 mol) was slowly added (ten minutes) to this solution by a syringe. The mixture was stirred at room temperature until the disappearance of ketone (monitored by thin layer chromatography). Then the mixture was poured into 50 ml brine and extracted with CH2Cl2 (40 ml). The organic layer was combined and dried over anhydrous Na2SO4. Removal of the solvent under reduced pressure and purification of the residue by recrystallization gave the title compound (2.1 g, yield 90%). The colourless crystals (average dimensions 0.3 mm × 0.2 mm × 0.2 mm) suitable for X-ray data collection were obtained by slow evaporation of a CH2Cl2 and MeOH solution in a ratio 4:1 at 293 K.

Refinement top

The difference electron density map has shown that the structure is disordered over two orientations in the E-ethen-1,2-yl group (C7 and C8 atoms). The H atoms could have been distinguished in the difference electron density maps, even in the disordered parts. The disordered parts were assumed to have the same geometry. The applied constraints: The sum of the occupancies of the disordered parts equaled to 1; the methyl as well as the aryl and the ethenyl H atoms were refined in idealized geometry with distances equal to 0.96, 0.93 and 0.93 Å, respectively. Uiso=1.2Ueq(Caryl/Cethenyl) and Uiso=1.5Ueq(Cmethyl). As to the restraints the pairs of the distances C8-C9 and C8-C9'; C1-C7 and C1-C7'; C7-C8 and C7-C8' were set to be as close possible by the command SADI with the effective standard uncertainty set to 0.001. The displacement parameters of C1, C7, C7', C8, C8', C9 were subjected to the restraint DELU 0.001 001.

From the refinement have been omitted diffractions 0 0 1; -2 0 2; -2 0 4, -1 0 2, -1 0 1 that did not match the model.

The refined occupational parameters of the disordered groups C7(H7)-C8(H8) and C7'(H7')-C8'(H8') converged to 0.568 (5) and 0.432 (5), respectively.

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SMART (Bruker, 1997); data reduction: SAINT (Bruker, 1999); 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
[Figure 1] Fig. 1. View of the title molecule disordered over two positions showing the atom-labelling scheme. The displacement ellipsoids are drawn at the 30% probability level. The H atoms are represented by spheres of arbitrary radius.
[Figure 2] Fig. 2. Intermolecular C—H···O interactions (dotted lines) in the title compound. [Symmetry code: 1 - x, 1 - y, 1 - z]
(E)-2-Methoxy-4-(3-oxobut-1-enyl)phenyl acetate top
Crystal data top
C13H14O4Z = 2
Mr = 234.24F(000) = 248
Triclinic, P1Dx = 1.267 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 6.2534 (5) ÅCell parameters from 1174 reflections
b = 7.5797 (5) Åθ = 3.8–27.7°
c = 13.9718 (8) ŵ = 0.09 mm1
α = 96.611 (2)°T = 299 K
β = 91.487 (2)°Block, colourless
γ = 110.599 (2)°0.30 × 0.23 × 0.20 mm
V = 614.21 (7) Å3
Data collection top
Bruker SMART 4K CCD area-detector
diffractometer
2381 independent reflections
Radiation source: fine-focus sealed tube1423 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.049
ϕ and ω scansθmax = 26.0°, θmin = 2.9°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1997)
h = 77
Tmin = 0.981, Tmax = 0.989k = 89
3984 measured reflectionsl = 1017
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)] = 0.066Hydrogen site location: difference Fourier map
wR(F2) = 0.220H-atom parameters constrained
S = 1.10 w = 1/[σ2(Fo2) + (0.1082P)2 + 0.0333P]
where P = (Fo2 + 2Fc2)/3
2381 reflections(Δ/σ)max = 0.001
173 parametersΔρmax = 0.23 e Å3
14 restraintsΔρmin = 0.47 e Å3
61 constraints
Crystal data top
C13H14O4γ = 110.599 (2)°
Mr = 234.24V = 614.21 (7) Å3
Triclinic, P1Z = 2
a = 6.2534 (5) ÅMo Kα radiation
b = 7.5797 (5) ŵ = 0.09 mm1
c = 13.9718 (8) ÅT = 299 K
α = 96.611 (2)°0.30 × 0.23 × 0.20 mm
β = 91.487 (2)°
Data collection top
Bruker SMART 4K CCD area-detector
diffractometer
2381 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1997)
1423 reflections with I > 2σ(I)
Tmin = 0.981, Tmax = 0.989Rint = 0.049
3984 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.06614 restraints
wR(F2) = 0.220H-atom parameters constrained
S = 1.10Δρmax = 0.23 e Å3
2381 reflectionsΔρmin = 0.47 e Å3
173 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*/UeqOcc. (<1)
C10.7293 (5)0.3948 (4)0.2545 (3)0.0882 (10)
C20.9194 (5)0.5292 (4)0.3052 (2)0.0738 (8)
H20.90740.57630.36850.089*
C31.1270 (4)0.5962 (3)0.26515 (19)0.0624 (7)
C41.1411 (4)0.5259 (3)0.16982 (19)0.0609 (7)
C50.9549 (5)0.3919 (4)0.1173 (2)0.0768 (8)
H50.96730.34600.05380.092*
C60.7504 (5)0.3261 (4)0.1588 (3)0.0937 (11)
H60.62410.23490.12320.112*
C70.4817 (6)0.2784 (6)0.2726 (3)0.0590 (12)0.568 (5)
H70.38090.18600.22670.071*0.568 (5)
C80.4287 (6)0.3213 (5)0.3572 (2)0.0590 (12)0.568 (5)
H80.53500.41570.40060.071*0.568 (5)
C7'0.5396 (6)0.3583 (5)0.3256 (2)0.0695 (19)0.432 (5)
H7'0.56590.43480.38490.083*0.432 (5)
C8'0.3469 (9)0.2245 (8)0.3042 (3)0.0690 (17)0.432 (5)
H8'0.30870.14330.24620.083*0.432 (5)
C90.1831 (5)0.2135 (5)0.3871 (3)0.0823 (9)
C100.0103 (8)0.0611 (5)0.3285 (3)0.1215 (14)
H10A0.14000.02130.36680.182*
H10B0.03490.04520.30820.182*
H10C0.05060.10900.27280.182*
C111.3290 (6)0.7714 (5)0.4125 (2)0.0957 (10)
H11A1.23090.84250.42720.144*
H11B1.48300.84660.43710.144*
H11C1.27710.65680.44200.144*
C121.4400 (5)0.7588 (4)0.10439 (18)0.0678 (7)
C131.6743 (5)0.7974 (5)0.0730 (2)0.0937 (10)
H13A1.67240.69990.02220.141*
H13B1.77410.79860.12660.141*
H13C1.72860.91870.04970.141*
O10.1650 (4)0.2704 (4)0.46647 (19)0.1071 (8)
O21.3230 (3)0.7243 (3)0.31006 (13)0.0802 (6)
O31.3305 (3)0.8606 (3)0.10693 (14)0.0814 (6)
O41.3533 (3)0.5806 (2)0.13013 (12)0.0693 (6)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0607 (15)0.0758 (16)0.144 (2)0.0288 (13)0.0191 (15)0.0587 (17)
C20.0849 (16)0.0753 (14)0.0869 (16)0.0450 (13)0.0302 (12)0.0313 (12)
C30.0681 (13)0.0545 (11)0.0715 (14)0.0262 (10)0.0083 (11)0.0124 (10)
C40.0657 (13)0.0539 (11)0.0710 (14)0.0260 (10)0.0114 (10)0.0120 (10)
C50.0794 (16)0.0613 (13)0.0850 (16)0.0210 (12)0.0046 (12)0.0102 (11)
C60.0754 (17)0.0681 (15)0.127 (2)0.0162 (13)0.0100 (16)0.0285 (15)
C70.071 (3)0.047 (2)0.056 (2)0.022 (2)0.007 (2)0.0067 (18)
C80.069 (4)0.060 (3)0.051 (3)0.024 (3)0.001 (2)0.003 (2)
C8'0.075 (4)0.072 (4)0.059 (4)0.029 (3)0.015 (3)0.009 (3)
C7'0.061 (4)0.046 (3)0.067 (5)0.019 (3)0.001 (3)0.006 (3)
C90.0968 (19)0.0915 (17)0.0871 (18)0.0544 (16)0.0341 (15)0.0406 (15)
C100.170 (3)0.105 (2)0.111 (2)0.077 (2)0.014 (2)0.0052 (17)
C110.118 (2)0.1023 (18)0.0702 (16)0.0465 (16)0.0048 (13)0.0076 (13)
C120.0737 (14)0.0587 (13)0.0602 (13)0.0164 (11)0.0068 (10)0.0040 (9)
C130.0821 (17)0.0900 (17)0.1022 (19)0.0205 (14)0.0215 (13)0.0031 (13)
O10.1010 (13)0.1159 (14)0.0938 (13)0.0276 (11)0.0235 (10)0.0089 (11)
O20.0838 (11)0.0797 (10)0.0694 (10)0.0189 (9)0.0060 (7)0.0027 (7)
O30.0893 (11)0.0624 (9)0.0981 (12)0.0285 (9)0.0171 (8)0.0156 (8)
O40.0753 (10)0.0609 (9)0.0759 (10)0.0279 (7)0.0172 (7)0.0076 (7)
Geometric parameters (Å, º) top
C1—C21.375 (4)C7'—H7'0.9300
C1—C61.405 (5)C8'—C91.556 (4)
C1—C71.533 (4)C8'—H8'0.9300
C1—C7'1.538 (4)C9—O11.166 (3)
C2—C31.377 (4)C9—C101.488 (5)
C2—H20.9300C10—H10A0.9600
C3—O21.349 (3)C10—H10B0.9600
C3—C41.393 (3)C10—H10C0.9600
C4—C51.370 (4)C11—O21.431 (3)
C4—O41.395 (3)C11—H11A0.9600
C5—C61.370 (4)C11—H11B0.9600
C5—H50.9300C11—H11C0.9600
C6—H60.9300C12—O31.197 (3)
C7—C81.273 (3)C12—O41.362 (3)
C7—H70.9300C12—C131.479 (4)
C8—C91.559 (4)C13—H13A0.9600
C8—H80.9300C13—H13B0.9600
C7'—C8'1.274 (4)C13—H13C0.9600
C2—C1—C6118.2 (3)C7'—C8'—H8'124.2
C2—C1—C7138.3 (3)C9—C8'—H8'124.2
C6—C1—C7103.5 (3)O1—C9—C10121.7 (3)
C2—C1—C7'105.1 (3)O1—C9—C8'145.9 (3)
C6—C1—C7'136.7 (3)C10—C9—C8'92.4 (3)
C1—C2—C3122.0 (3)O1—C9—C8109.7 (3)
C1—C2—H2119.0C10—C9—C8128.6 (3)
C3—C2—H2119.0C9—C10—H10A109.5
O2—C3—C2126.0 (3)C9—C10—H10B109.5
O2—C3—C4115.8 (2)H10A—C10—H10B109.5
C2—C3—C4118.2 (3)C9—C10—H10C109.5
C5—C4—C3121.3 (2)H10A—C10—H10C109.5
C5—C4—O4119.3 (2)H10B—C10—H10C109.5
C3—C4—O4119.2 (2)O2—C11—H11A109.5
C4—C5—C6119.6 (3)O2—C11—H11B109.5
C4—C5—H5120.2H11A—C11—H11B109.5
C6—C5—H5120.2O2—C11—H11C109.5
C5—C6—C1120.8 (3)H11A—C11—H11C109.5
C5—C6—H6119.6H11B—C11—H11C109.5
C1—C6—H6119.6O3—C12—O4121.7 (2)
C8—C7—C1112.9 (2)O3—C12—C13128.1 (3)
C8—C7—H7123.6O4—C12—C13110.2 (3)
C1—C7—H7123.6C12—C13—H13A109.5
C7—C8—C9119.1 (3)C12—C13—H13B109.5
C7—C8—H8120.5H13A—C13—H13B109.5
C9—C8—H8120.5C12—C13—H13C109.5
C8'—C7'—C1120.7 (3)H13A—C13—H13C109.5
C8'—C7'—H7'119.6H13B—C13—H13C109.5
C1—C7'—H7'119.6C3—O2—C11117.5 (2)
C7'—C8'—C9111.7 (2)C12—O4—C4118.03 (19)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C2—H2···O1i0.932.583.507 (4)172
Symmetry code: (i) x+1, y+1, z+1.

Experimental details

Crystal data
Chemical formulaC13H14O4
Mr234.24
Crystal system, space groupTriclinic, P1
Temperature (K)299
a, b, c (Å)6.2534 (5), 7.5797 (5), 13.9718 (8)
α, β, γ (°)96.611 (2), 91.487 (2), 110.599 (2)
V3)614.21 (7)
Z2
Radiation typeMo Kα
µ (mm1)0.09
Crystal size (mm)0.30 × 0.23 × 0.20
Data collection
DiffractometerBruker SMART 4K CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1997)
Tmin, Tmax0.981, 0.989
No. of measured, independent and
observed [I > 2σ(I)] reflections
3984, 2381, 1423
Rint0.049
(sin θ/λ)max1)0.617
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.066, 0.220, 1.10
No. of reflections2381
No. of parameters173
No. of restraints14
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.23, 0.47

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1999), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C2—H2···O1i0.932.583.507 (4)171.6
Symmetry code: (i) x+1, y+1, z+1.
 

Acknowledgements

The authors are grateful to Xiangfan University for financial support.

References

First citationBruker (1997). SMART. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationBruker (1999). SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationBuszek, K. R. & Brown, N. (2007). Org. Lett. 9, 707–710.  Web of Science CrossRef PubMed CAS Google Scholar
First citationEtter, M. C., MacDonald, J. C. & Bernstein, J. (1990). Acta Cryst. B46, 256–262.  CrossRef CAS Web of Science IUCr Journals Google Scholar
First citationKuo, P.-C., Damu, A. G., Cherng, C.-Y., Jeng, J.-F., Teng, C.-M., Lee, E.-J. & Wu, T.-S. (2005). Arch. Pharm. Res. 28, 518–528.  Web of Science CrossRef PubMed CAS Google Scholar
First citationSheldrick, G. M. (1997). SADABS. University of Göttingen, Germany.  Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationSteiner, T. & Desiraju, G. R. (1998). Chem. Commun. pp. 891–892.  Web of Science CrossRef Google Scholar
First citationYarishkin, O. V., Ryu, H. W., Park, J.-Y., Yang, M. S., Hong, S.-G. & Park, K. H. (2008). Bioorg. Med. Chem. Lett. 18, 137–140.  Web of Science CrossRef PubMed CAS Google Scholar

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