Ethyl (E)-4-(2-acetyl­phen­oxy)but-2-enoate

Williamson, C.; Storey, J.M.D.; Harrison, W.T.A.

doi:10.1107/S1600536807007969

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 63| Part 3| March 2007| Pages o1428-o1429

https://doi.org/10.1107/S1600536807007969

Ethyl (E)-4-(2-acetylphenoxy)but-2-enoate

Craig Williamson,^a John M. D. Storey ^a and William T. A. Harrison ^a ^*

^aDepartment of Chemistry, University of Aberdeen, Meston Walk, Aberdeen AB24 3UE, Scotland
^*Correspondence e-mail: w.harrison@abdn.ac.uk

(Received 15 February 2007; accepted 16 February 2007; online 23 February 2007)

The crystal packing in the title compound, C₁₄H₁₆O₄, is controlled by van der Waals interactions.

Comment

The title compound, (I) (Fig. 1), was prepared as part of our ongoing studies of cyclization reactions (Williamson et al., 2007 ). The dihedral angles between the mean plane of the C3–C8 benzene ring and the planes of the C1/C2/O1 and the C12/O3/O4 groups are 4.26 (6) and 9.63 (12)°, respectively. The C11—C12 bond length of 1.4787 (16) Å implies that there is little, if any, delocalization of electrons between the C12/O3/O4 and C10/C11 groups in the side chain. A similar result was found for the equivalent bond in ethyl (E)-4-(2-formylphenoxy)but-2-enoate (Williamson et al., 2005 ). Otherwise, the geometrical parameters for (I) may be regarded as normal (Allen et al., 1987 ).

There are no clear-cut directional intermolecular bonding interactions in the crystal structure of (I). The minimum separation of the centroids of the benzene rings of nearby molecules is greater than 5.4 Å.

Figure 1
View of the molecular structure of (I)

, showing 50% displacement ellipsoids. H atoms are drawn as small spheres of arbitrary radius.

Experimental

A dry two-necked flask was charged with NaH (0.360 g, 15 mmol) and washed with dry petrol (3 × 1 ml). Dry DMF (40 ml) was added, and the suspension cooled to 273 K. 2-Hydroxyacetophenone (1.361 g, 1.20 ml, 10 mmol) was added and the solution stirred for 20 min. Ethyl 4-bromocrotonate (2.82 g, 2.01 ml, 11 mmol) was added in one portion. The solution was allowed to warm to room temperature, and stirred for 18 h. H₂O (60 ml) was added, followed by extraction with Et₂O (3 × 50 ml). The combined organics were washed with saturated brine (75 ml), dried over MgSO₄, and the solvent removed in vacuo. Chromatographic elution with 20% EtOAc in hexane, and collecting the fraction with R_F = 0.22 yielded the desired product as colourless needles (1.263 g, 51%), which were recrystallized from EtOH; analysis calculated for C₁₄H₁₆O₄: C 67.73, H 6.50%; found C 67.61, H 6.59%;

Crystal data

C₁₄H₁₆O₄
M_r = 248.27
Monoclinic, C 2/c
a = 23.7480 (8) Å
b = 7.2686 (3) Å
c = 15.8710 (4) Å
β = 112.2400 (13)°
V = 2535.76 (15) Å³
Z = 8
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 120 (2) K
0.48 × 0.42 × 0.24 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1999 ) T_min = 0.956, T_max = 0.978
25327 measured reflections
2909 independent reflections
2396 reflections with I > 2σ(I)
R_int = 0.032

Refinement

R[F² > 2σ(F²)] = 0.038
wR(F²) = 0.105
S = 1.06
2909 reflections
166 parameters
H-atom parameters constrained
Δρ_max = 0.22 e Å⁻³
Δρ_min = −0.21 e Å⁻³

All H atoms were placed in calculated positions (C—H = 0.95–0.99 Å) and refined as riding, with U_iso(H) = 1.2U_eq(C) or 1.5U_eq(methyl C). The methyl groups were allowed to rotate but not to tip, to best fit the electron density.

Data collection: COLLECT (Nonius, 1998 ); cell refinement: SCALEPACK (Otwinowski & Minor, 1997 ); data reduction: SCALEPACK and DENZO (Otwinowski & Minor, 1997), and SORTAV (Blessing, 1995 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536807007969/xu2213sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536807007969/xu2213Isup2.hkl

Computing details top

Data collection: COLLECT (Nonius, 1998); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: SCALEPACK and SCALEPACK (Otwinowski & Minor, 1997), and SORTAV (Blessing, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97.

Ethyl (E)-4-(2-acetylphenoxy)but-2-enoate top

Crystal data top

C₁₄H₁₆O₄	F(000) = 1056
M_r = 248.27	D_x = 1.301 Mg m⁻³
Monoclinic, C2/c	Melting point = 325–327 K
Hall symbol: -C 2yc	Mo Kα radiation, λ = 0.71073 Å
a = 23.7480 (8) Å	Cell parameters from 5501 reflections
b = 7.2686 (3) Å	θ = 2.9–27.5°
c = 15.8710 (4) Å	µ = 0.10 mm⁻¹
β = 112.2400 (13)°	T = 120 K
V = 2535.76 (15) Å³	Block, colourless
Z = 8	0.48 × 0.42 × 0.24 mm

Data collection top

Nonius KappaCCD diffractometer	2909 independent reflections
Radiation source: fine-focus sealed tube	2396 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.032
ω and φ scans	θ_max = 27.5°, θ_min = 2.9°
Absorption correction: multi-scan (SADABS; Bruker, 1999)	h = −30→30
T_min = 0.956, T_max = 0.978	k = −9→8
25327 measured reflections	l = −20→20

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.038	H-atom parameters constrained
wR(F²) = 0.105	w = 1/[σ²(F_o²) + (0.0568P)² + 0.9651P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max < 0.001
2909 reflections	Δρ_max = 0.22 e Å⁻³
166 parameters	Δρ_min = −0.21 e Å⁻³
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0042 (10)

Special details top

Experimental. ν_max(KBr)/cm^-1 2971 (Ar), 2893 [C=O (aldehyde)], 1704 [C=O (ester)], 1646 [C=O (aldehyde)].

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

	x	y	z	U_iso*/U_eq
C1	0.22000 (5)	0.97136 (16)	−0.10660 (7)	0.0291 (3)
H1A	0.2045	0.9573	−0.1729	0.044*
H1B	0.1934	1.0545	−0.0900	0.044*
H1C	0.2210	0.8510	−0.0783	0.044*
C2	0.28295 (5)	1.04987 (14)	−0.07388 (7)	0.0256 (3)
C3	0.31980 (5)	1.07664 (14)	0.02575 (7)	0.0237 (2)
C4	0.37937 (5)	1.13971 (16)	0.04821 (8)	0.0301 (3)
H4	0.3939	1.1595	0.0008	0.036*
C5	0.41776 (6)	1.17410 (18)	0.13700 (8)	0.0343 (3)
H5	0.4578	1.2186	0.1503	0.041*
C6	0.39703 (5)	1.14285 (16)	0.20640 (8)	0.0305 (3)
H6	0.4232	1.1656	0.2677	0.037*
C7	0.33858 (5)	1.07876 (15)	0.18729 (7)	0.0255 (2)
H7	0.3250	1.0569	0.2355	0.031*
C8	0.29952 (5)	1.04603 (14)	0.09738 (7)	0.0219 (2)
C9	0.22103 (5)	0.95766 (16)	0.14867 (7)	0.0261 (3)
H9A	0.2231	1.0753	0.1811	0.031*
H9B	0.2481	0.8682	0.1924	0.031*
C10	0.15761 (5)	0.88752 (15)	0.11317 (7)	0.0271 (3)
H10	0.1412	0.8564	0.1574	0.033*
C11	0.12123 (5)	0.86334 (15)	0.02712 (7)	0.0275 (3)
H11	0.1356	0.8877	−0.0201	0.033*
C12	0.05817 (5)	0.79840 (15)	0.00437 (8)	0.0285 (3)
C13	−0.03758 (5)	0.75614 (18)	−0.11551 (9)	0.0345 (3)
H13A	−0.0562	0.8164	−0.0765	0.041*
H13B	−0.0420	0.6213	−0.1117	0.041*
C14	−0.06821 (6)	0.8193 (2)	−0.21187 (9)	0.0422 (3)
H14A	−0.1118	0.7926	−0.2332	0.063*
H14B	−0.0507	0.7546	−0.2504	0.063*
H14C	−0.0622	0.9521	−0.2152	0.063*
O1	0.30498 (4)	1.09337 (13)	−0.12924 (5)	0.0368 (2)
O2	0.24104 (3)	0.98547 (10)	0.07529 (5)	0.0247 (2)
O3	0.02650 (4)	0.80537 (11)	−0.08531 (5)	0.0317 (2)
O4	0.03676 (4)	0.74967 (14)	0.05879 (6)	0.0431 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0401 (7)	0.0312 (6)	0.0162 (5)	0.0016 (5)	0.0107 (5)	0.0001 (4)
C2	0.0370 (6)	0.0242 (5)	0.0189 (5)	0.0078 (4)	0.0143 (5)	0.0023 (4)
C3	0.0312 (6)	0.0232 (5)	0.0195 (5)	0.0051 (4)	0.0127 (4)	0.0025 (4)
C4	0.0342 (6)	0.0352 (6)	0.0262 (6)	0.0024 (5)	0.0173 (5)	0.0030 (5)
C5	0.0281 (6)	0.0435 (7)	0.0318 (6)	−0.0007 (5)	0.0119 (5)	0.0015 (5)
C6	0.0306 (6)	0.0360 (6)	0.0217 (5)	0.0014 (5)	0.0062 (5)	0.0006 (5)
C7	0.0319 (6)	0.0282 (6)	0.0175 (5)	0.0035 (4)	0.0107 (4)	0.0024 (4)
C8	0.0266 (5)	0.0207 (5)	0.0193 (5)	0.0038 (4)	0.0097 (4)	0.0017 (4)
C9	0.0342 (6)	0.0303 (6)	0.0175 (5)	0.0006 (4)	0.0138 (4)	0.0016 (4)
C10	0.0343 (6)	0.0279 (5)	0.0247 (5)	0.0000 (5)	0.0174 (5)	0.0019 (4)
C11	0.0324 (6)	0.0292 (6)	0.0253 (5)	0.0000 (5)	0.0158 (5)	0.0012 (4)
C12	0.0353 (6)	0.0274 (6)	0.0256 (6)	−0.0019 (5)	0.0147 (5)	−0.0006 (4)
C13	0.0293 (6)	0.0383 (6)	0.0376 (7)	−0.0067 (5)	0.0146 (5)	−0.0022 (5)
C14	0.0332 (7)	0.0477 (8)	0.0414 (7)	−0.0044 (6)	0.0093 (6)	0.0013 (6)
O1	0.0454 (5)	0.0494 (5)	0.0221 (4)	0.0018 (4)	0.0201 (4)	0.0029 (4)
O2	0.0285 (4)	0.0325 (4)	0.0153 (4)	−0.0011 (3)	0.0108 (3)	0.0006 (3)
O3	0.0297 (4)	0.0412 (5)	0.0260 (4)	−0.0049 (3)	0.0126 (3)	0.0004 (3)
O4	0.0452 (5)	0.0591 (6)	0.0309 (5)	−0.0168 (5)	0.0212 (4)	0.0005 (4)

Geometric parameters (Å, º) top

C1—C2	1.4974 (16)	C9—O2	1.4289 (12)
C1—H1A	0.9800	C9—C10	1.4844 (16)
C1—H1B	0.9800	C9—H9A	0.9900
C1—H1C	0.9800	C9—H9B	0.9900
C2—O1	1.2222 (13)	C10—C11	1.3225 (16)
C2—C3	1.5021 (14)	C10—H10	0.9500
C3—C4	1.3990 (16)	C11—C12	1.4787 (16)
C3—C8	1.4099 (14)	C11—H11	0.9500
C4—C5	1.3810 (17)	C12—O4	1.2093 (14)
C4—H4	0.9500	C12—O3	1.3355 (14)
C5—C6	1.3848 (16)	C13—O3	1.4564 (14)
C5—H5	0.9500	C13—C14	1.4956 (18)
C6—C7	1.3845 (16)	C13—H13A	0.9900
C6—H6	0.9500	C13—H13B	0.9900
C7—C8	1.3969 (14)	C14—H14A	0.9800
C7—H7	0.9500	C14—H14B	0.9800
C8—O2	1.3701 (13)	C14—H14C	0.9800

C2—C1—H1A	109.5	O2—C9—H9A	109.7
C2—C1—H1B	109.5	C10—C9—H9A	109.7
H1A—C1—H1B	109.5	O2—C9—H9B	109.7
C2—C1—H1C	109.5	C10—C9—H9B	109.7
H1A—C1—H1C	109.5	H9A—C9—H9B	108.2
H1B—C1—H1C	109.5	C11—C10—C9	127.59 (10)
O1—C2—C1	119.47 (10)	C11—C10—H10	116.2
O1—C2—C3	119.08 (10)	C9—C10—H10	116.2
C1—C2—C3	121.45 (9)	C10—C11—C12	120.00 (10)
C4—C3—C8	117.86 (9)	C10—C11—H11	120.0
C4—C3—C2	116.14 (9)	C12—C11—H11	120.0
C8—C3—C2	125.99 (10)	O4—C12—O3	123.56 (11)
C5—C4—C3	122.18 (10)	O4—C12—C11	125.43 (10)
C5—C4—H4	118.9	O3—C12—C11	110.98 (9)
C3—C4—H4	118.9	O3—C13—C14	107.72 (10)
C4—C5—C6	119.07 (11)	O3—C13—H13A	110.2
C4—C5—H5	120.5	C14—C13—H13A	110.2
C6—C5—H5	120.5	O3—C13—H13B	110.2
C7—C6—C5	120.64 (10)	C14—C13—H13B	110.2
C7—C6—H6	119.7	H13A—C13—H13B	108.5
C5—C6—H6	119.7	C13—C14—H14A	109.5
C6—C7—C8	120.28 (10)	C13—C14—H14B	109.5
C6—C7—H7	119.9	H14A—C14—H14B	109.5
C8—C7—H7	119.9	C13—C14—H14C	109.5
O2—C8—C7	122.21 (9)	H14A—C14—H14C	109.5
O2—C8—C3	117.82 (9)	H14B—C14—H14C	109.5
C7—C8—C3	119.96 (10)	C8—O2—C9	117.03 (8)
O2—C9—C10	109.98 (8)	C12—O3—C13	116.00 (9)

O1—C2—C3—C4	−4.09 (15)	C4—C3—C8—C7	0.02 (15)
C1—C2—C3—C4	175.94 (10)	C2—C3—C8—C7	−179.23 (10)
O1—C2—C3—C8	175.16 (10)	O2—C9—C10—C11	−4.35 (16)
C1—C2—C3—C8	−4.80 (16)	C9—C10—C11—C12	−177.61 (10)
C8—C3—C4—C5	−0.79 (17)	C10—C11—C12—O4	−6.17 (18)
C2—C3—C4—C5	178.53 (10)	C10—C11—C12—O3	171.96 (10)
C3—C4—C5—C6	0.92 (18)	C7—C8—O2—C9	0.38 (14)
C4—C5—C6—C7	−0.27 (18)	C3—C8—O2—C9	−179.16 (9)
C5—C6—C7—C8	−0.48 (17)	C10—C9—O2—C8	−178.45 (8)
C6—C7—C8—O2	−178.93 (10)	O4—C12—O3—C13	2.08 (17)
C6—C7—C8—C3	0.60 (16)	C11—C12—O3—C13	−176.09 (9)
C4—C3—C8—O2	179.57 (9)	C14—C13—O3—C12	165.19 (10)
C2—C3—C8—O2	0.32 (15)

Acknowledgements

We thank the EPSRC National Crystallography Service (University of Southampton) for the data collection.

References

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