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

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

doi:10.1107/S1600536805013164

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 61| Part 6| June 2005| Pages o1566-o1568

https://doi.org/10.1107/S1600536805013164

Ethyl (E)-4-(2-formylphenoxy)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 21 April 2005; accepted 26 April 2005; online 7 May 2005)

The molecule of the title compound, C₁₃H₁₄O₄, possesses normal geometric parameters. Its approximately planar conformation could be influenced by two intramolecular C—H⋯O interactions.

Comment

The title compound, (I), was prepared as a test substrate for an investigation into potential catalysts for the intramolecular Stetter reaction. The compound is well known and has been previously used in this context (Kerr et al., 2002 ). In the present work, the synthesis used was that of Gong et al. (1998 ).

The molecule of compound (I) possesses normal geometric parameters (Table 1). The complete molecule is approximately planar (for the non-H atoms, the r.m.s deviation from the least-squares plane is 0.100 Å). This conformation might be stabilized by two intramolecular C—H⋯O interactions (Fig. 1, Table 2). The acute O—H⋯O bond angles are consistent with the intramolecular nature of these putative bonds. The r.m.s. deviation from the mean plane for atoms C1, C2, C7, C8, C9, C10 and O2 is 0.043 Å [maximum deviation 0.1005 (11) Å for O2].

There are no π–π stacking or other weak intermolecular interactions in (I) and the crystal packing (Fig. 2) is controlled by van der Waals forces.

Figure 1
A view of (I)

, showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are drawn as small spheres of arbitrary radi. The possible C—H⋯O interactions are indicated by dashed lines.

Figure 2
The unit-cell packing in (I)

, viewed down [010]. Displacement ellipsoids are drawn at the 50% probability level and H atoms have been omitted for clarity.

Experimental

A dry two-necked flask was charged with NaH (15 mmol, 360.4 mg). Dry dimethylformamide (40 ml) was added and the resulting suspension cooled to 273 K. Salicylaldehyde (10 mmol, 1.220 g, 1.06 ml) was added and the solution stirred for 20 min. Ethyl 4-bromocrotonate (11 mmol, 2.82 g, 2.01 ml) was added in one portion. The solution was then allowed to warm to room temperature and stirred for 1 h. Water (60 ml) was added, followed by extraction with Et₂O (3 × 50 ml). The combined organic phases were washed with saturated brine (75 ml), dried (MgSO₄) and the solvent removed. Chromatography of the resulting solid in 10% EtOAc in hexane allowed collection of the desired product (1.809 g, 77.2%), which was recrystallized from ethanol as colourless blocks or plates; m.p 342–344 K. Analysis, C₁₃H₁₄O₄ requires: C 66.66, H 6.02%; found: C 66.53, H 6.00%. Spectroscopic analysis: IR (KBr, ν_max, cm⁻¹): 2975.6 (Ar), 2902.4 (CH), 2859.5 (CHO), 1709.4 (CO₂Et), 1671 (CHO); ¹H NMR (250 MHz, CDCl₃, δ, p.p.m.); 10.5 (1H, s, CHO), 7.8 (1H, d, J = 8 Hz, Ph), 7.6 (1H, t, J = 8 Hz, Ph), 7.0 (3H, m), 6.2 (1H, d, J = 15 Hz, CH—CO₂Et), 4.8 (2H, s, CH₂), 4.2 (2H, q, J = 7 Hz, CH₂), 1.3 (3H, t, J = 8 Hz, Me); ¹³C NMR (250 MHz, CDCl₃, δ, p.p.m.) 189.3 (CHO), 165.8 (CO₂Et), 160.2, 141.2, 135.9, 128.8, 125.1, 122.5, 121.4, 112.5, 66.8 (CH₂), 60.7 (CH₂), 14.2 (Me); MS (ESI⁺): calculated: m/z 252.1230; found: 252.1232 [M+NH₄⁺].

Crystal data

C₁₃H₁₄O₄
M_r = 234.24
Monoclinic, P 2₁ /c
a = 10.6759 (6) Å
b = 6.9487 (4) Å
c = 16.4346 (6) Å
β = 102.164 (3)°
V = 1191.81 (11) Å³
Z = 4
D_x = 1.305 Mg m⁻³
Mo Kα radiation
Cell parameters from 2702 reflections
θ = 2.9–27.5°
μ = 0.10 mm⁻¹
T = 120 (2) K
Plate, colourless
0.46 × 0.27 × 0.09 mm

Data collection

Nonius KappaCCD area-detector diffractometer
ω and φ scans
Absorption correction: multi-scan(SADABS; Bruker, 2003 )T_min = 0.957, T_max = 0.993
10 415 measured reflections
2712 independent reflections
1830 reflections with I > 2σ(I)
R_int = 0.052
θ_max = 27.5°
h = −13 → 13
k = −8 → 8
l = −17 → 21

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.048
wR(F²) = 0.126
S = 1.02
2712 reflections
156 parameters
H-atom parameters constrained
w = 1/[σ²(F_o²) + (0.059P)² + 0.2428P] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max = 0.002
Δρ_max = 0.20 e Å⁻³
Δρ_min = −0.21 e Å⁻³
Extinction correction: SHELXL97 (Sheldrick, 1997 )
Extinction coefficient: 0.036 (5)

Table 1
Selected torsion angles (°)

O1—C1—C2—C7	179.50 (15)
C1—C2—C7—O2	−1.2 (2)
O2—C8—C9—C10	5.2 (2)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1⋯O2	0.95	2.39	2.7353 (17)	101
C10—H10⋯O2	0.95	2.38	2.7221 (19)	101

All H atoms were placed in calculated positions, with C—H distances in the range 0.95–0.99 Å, and refined as riding on their carrier atoms, with U_iso(H) = 1.2U_eq(C) or 1.5U_eq(methyl C).

Data collection: COLLECT (Nonius, 1998 ); cell refinement: SCALEPACK (Otwinowski & Minor 1997 ); data reduction: DENZO (Otwinowski & Minor 1997) and SCALEPACK; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP3 (Farrugia, 1997 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536805013164/ci6571sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536805013164/ci6571Isup2.hkl

Computing details top

Data collection: COLLECT (Nonius, 1998); cell refinement: SCALEPACK (Otwinowski & Minor 1997); data reduction: DENZO (Otwinowski & Minor 1997) and SCALEPACK; 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-formylphenoxy)but-2-enoate top

Crystal data top

C₁₃H₁₄O₄	F(000) = 496
M_r = 234.24	D_x = 1.305 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2702 reflections
a = 10.6759 (6) Å	θ = 2.9–27.5°
b = 6.9487 (4) Å	µ = 0.10 mm⁻¹
c = 16.4346 (6) Å	T = 120 K
β = 102.164 (3)°	Plate, colourless
V = 1191.81 (11) Å³	0.46 × 0.27 × 0.09 mm
Z = 4

Data collection top

Nonius KappaCCD area-detector diffractometer	2712 independent reflections
Radiation source: fine-focus sealed tube	1830 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.052
ω and φ scans	θ_max = 27.5°, θ_min = 3.2°
Absorption correction: multi-scan (SADABS; Bruker, 2003)	h = −13→13
T_min = 0.957, T_max = 0.993	k = −8→8
10415 measured reflections	l = −17→21

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)] = 0.048	H-atom parameters constrained
wR(F²) = 0.126	w = 1/[σ²(F_o²) + (0.059P)² + 0.2428P] where P = (F_o² + 2F_c²)/3
S = 1.02	(Δ/σ)_max = 0.002
2712 reflections	Δρ_max = 0.20 e Å⁻³
156 parameters	Δρ_min = −0.21 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.036 (5)

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

	x	y	z	U_iso*/U_eq
C1	0.00191 (16)	0.2643 (2)	0.41727 (9)	0.0290 (4)
H1	0.0776	0.2147	0.4520	0.035*
C2	−0.10653 (15)	0.3112 (2)	0.45585 (9)	0.0241 (4)
C3	−0.21906 (16)	0.3879 (2)	0.40804 (10)	0.0323 (4)
H3	−0.2253	0.4080	0.3501	0.039*
C4	−0.32119 (17)	0.4351 (3)	0.44321 (11)	0.0381 (5)
H4	−0.3973	0.4875	0.4101	0.046*
C5	−0.31130 (17)	0.4051 (3)	0.52753 (11)	0.0362 (4)
H5	−0.3817	0.4367	0.5520	0.043*
C6	−0.20042 (16)	0.3297 (2)	0.57726 (10)	0.0305 (4)
H6	−0.1947	0.3112	0.6352	0.037*
C7	−0.09813 (14)	0.2818 (2)	0.54104 (9)	0.0236 (4)
C8	0.03522 (15)	0.1948 (3)	0.67211 (8)	0.0283 (4)
H8A	−0.0271	0.1052	0.6886	0.034*
H8B	0.0236	0.3234	0.6953	0.034*
C9	0.16789 (16)	0.1254 (2)	0.70449 (9)	0.0283 (4)
H9	0.1922	0.1012	0.7626	0.034*
C10	0.25501 (16)	0.0942 (2)	0.65988 (9)	0.0288 (4)
H10	0.2332	0.1142	0.6014	0.035*
C11	0.38551 (17)	0.0292 (2)	0.69836 (10)	0.0311 (4)
C12	0.59362 (17)	−0.0211 (3)	0.67090 (12)	0.0457 (5)
H12A	0.6030	−0.1177	0.7161	0.055*
H12B	0.6441	0.0943	0.6926	0.055*
C13	0.63992 (19)	−0.1017 (3)	0.59849 (14)	0.0503 (5)
H13A	0.7313	−0.1328	0.6154	0.075*
H13B	0.6273	−0.0066	0.5535	0.075*
H13C	0.5917	−0.2188	0.5790	0.075*
O1	0.00079 (12)	0.28500 (18)	0.34378 (6)	0.0387 (4)
O2	0.01446 (10)	0.20508 (16)	0.58333 (6)	0.0282 (3)
O3	0.45966 (11)	0.02940 (18)	0.64209 (7)	0.0357 (3)
O4	0.42190 (13)	−0.01633 (19)	0.77059 (7)	0.0443 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0347 (9)	0.0324 (10)	0.0205 (7)	−0.0045 (7)	0.0075 (7)	−0.0014 (7)
C2	0.0274 (8)	0.0226 (8)	0.0223 (7)	−0.0051 (7)	0.0053 (6)	−0.0022 (7)
C3	0.0352 (10)	0.0300 (10)	0.0291 (8)	−0.0030 (8)	0.0009 (7)	0.0018 (7)
C4	0.0293 (10)	0.0337 (11)	0.0481 (10)	0.0018 (8)	0.0010 (8)	0.0012 (8)
C5	0.0289 (9)	0.0320 (10)	0.0499 (11)	−0.0005 (8)	0.0135 (8)	−0.0059 (8)
C6	0.0344 (9)	0.0309 (10)	0.0287 (8)	−0.0063 (8)	0.0120 (7)	−0.0061 (7)
C7	0.0236 (8)	0.0224 (9)	0.0247 (8)	−0.0033 (6)	0.0047 (6)	−0.0022 (6)
C8	0.0361 (9)	0.0341 (10)	0.0157 (7)	−0.0016 (7)	0.0076 (6)	−0.0009 (7)
C9	0.0373 (10)	0.0280 (9)	0.0185 (7)	−0.0023 (7)	0.0033 (7)	0.0008 (7)
C10	0.0355 (9)	0.0287 (9)	0.0203 (7)	−0.0017 (7)	0.0017 (7)	−0.0002 (7)
C11	0.0362 (9)	0.0262 (9)	0.0291 (8)	−0.0007 (8)	0.0030 (7)	0.0000 (7)
C12	0.0294 (10)	0.0546 (13)	0.0514 (11)	0.0102 (9)	0.0046 (8)	0.0161 (10)
C13	0.0383 (11)	0.0352 (11)	0.0798 (14)	0.0004 (9)	0.0179 (10)	−0.0046 (11)
O1	0.0498 (8)	0.0489 (8)	0.0196 (6)	−0.0085 (6)	0.0123 (5)	−0.0011 (5)
O2	0.0291 (6)	0.0408 (7)	0.0150 (5)	0.0039 (5)	0.0055 (4)	0.0008 (5)
O3	0.0308 (7)	0.0403 (8)	0.0353 (6)	0.0053 (5)	0.0052 (5)	0.0068 (5)
O4	0.0456 (8)	0.0540 (9)	0.0292 (7)	0.0084 (6)	−0.0010 (5)	0.0094 (6)

Geometric parameters (Å, º) top

C1—O1	1.2138 (18)	C8—H8A	0.99
C1—C2	1.469 (2)	C8—H8B	0.99
C1—H1	0.95	C9—C10	1.318 (2)
C2—C3	1.395 (2)	C9—H9	0.95
C2—C7	1.399 (2)	C10—C11	1.474 (2)
C3—C4	1.377 (2)	C10—H10	0.95
C3—H3	0.95	C11—O4	1.2107 (19)
C4—C5	1.383 (3)	C11—O3	1.338 (2)
C4—H4	0.95	C12—O3	1.452 (2)
C5—C6	1.391 (2)	C12—C13	1.491 (3)
C5—H5	0.95	C12—H12A	0.99
C6—C7	1.390 (2)	C12—H12B	0.99
C6—H6	0.95	C13—H13A	0.98
C7—O2	1.3639 (18)	C13—H13B	0.98
C8—O2	1.4305 (16)	C13—H13C	0.98
C8—C9	1.485 (2)

O1—C1—C2	124.04 (16)	C9—C8—H8B	110.1
O1—C1—H1	118.0	H8A—C8—H8B	108.4
C2—C1—H1	118.0	C10—C9—C8	125.85 (14)
C3—C2—C7	119.04 (14)	C10—C9—H9	117.1
C3—C2—C1	120.33 (14)	C8—C9—H9	117.1
C7—C2—C1	120.63 (14)	C9—C10—C11	121.70 (14)
C4—C3—C2	121.23 (15)	C9—C10—H10	119.1
C4—C3—H3	119.4	C11—C10—H10	119.1
C2—C3—H3	119.4	O4—C11—O3	124.30 (16)
C3—C4—C5	118.99 (16)	O4—C11—C10	125.43 (17)
C3—C4—H4	120.5	O3—C11—C10	110.26 (13)
C5—C4—H4	120.5	O3—C12—C13	107.47 (15)
C4—C5—C6	121.41 (16)	O3—C12—H12A	110.2
C4—C5—H5	119.3	C13—C12—H12A	110.2
C6—C5—H5	119.3	O3—C12—H12B	110.2
C7—C6—C5	119.11 (15)	C13—C12—H12B	110.2
C7—C6—H6	120.4	H12A—C12—H12B	108.5
C5—C6—H6	120.4	C12—C13—H13A	109.5
O2—C7—C6	124.26 (14)	C12—C13—H13B	109.5
O2—C7—C2	115.53 (13)	H13A—C13—H13B	109.5
C6—C7—C2	120.22 (15)	C12—C13—H13C	109.5
O2—C8—C9	108.23 (12)	H13A—C13—H13C	109.5
O2—C8—H8A	110.1	H13B—C13—H13C	109.5
C9—C8—H8A	110.1	C7—O2—C8	118.02 (12)
O2—C8—H8B	110.1	C11—O3—C12	117.39 (13)

O1—C1—C2—C3	−1.2 (3)	C1—C2—C7—C6	178.90 (15)
O1—C1—C2—C7	179.50 (15)	O2—C8—C9—C10	5.2 (2)
C7—C2—C3—C4	0.1 (2)	C8—C9—C10—C11	178.58 (15)
C1—C2—C3—C4	−179.18 (16)	C9—C10—C11—O4	6.4 (3)
C2—C3—C4—C5	−0.1 (3)	C9—C10—C11—O3	−172.88 (16)
C3—C4—C5—C6	0.4 (3)	C6—C7—O2—C8	−8.0 (2)
C4—C5—C6—C7	−0.7 (3)	C2—C7—O2—C8	172.08 (13)
C5—C6—C7—O2	−179.24 (15)	C9—C8—O2—C7	−174.39 (13)
C5—C6—C7—C2	0.7 (2)	O4—C11—O3—C12	−2.6 (3)
C3—C2—C7—O2	179.52 (14)	C10—C11—O3—C12	176.75 (15)
C1—C2—C7—O2	−1.2 (2)	C13—C12—O3—C11	153.40 (15)
C3—C2—C7—C6	−0.4 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···O2	0.95	2.39	2.7353 (17)	101
C10—H10···O2	0.95	2.38	2.7221 (19)	101

Acknowledgements

The authors thank the EPSRC National Crystallography Service (University of Southampton) for the data collection and the EPSRC National Mass Spectrometry Service Centre (University of Swansea) for the high resolution mass spectroscopy data.

References

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