Methyl (E)-3-(2-formyl­phen­­oxy)acrylate

In the title compound, C₁₁H₁₀O₄, the methyl acrylate sub­stituent adopts an extended E conformation with all torsion angles close to 180°. The conformation of the keto group with respect to the olefinic double bond is typically S-trans. In the crystal, mol­ecules are linked via pairs of C—H⋯O hydrogen bonds, forming inversion dimers with an R₂²(8) graph-set motif. The dimers are further linked via C—H⋯O hydrogen bonds, forming chains along [001], which enclose R₃²(16) graph-set ring motifs. The keto group O atomaccepts two C—H⋯O interactions.

Related literature

For applications of acrylate derivatives, see: Xiao et al. (2008); De et al. (2011); Sharma (2011). For related crystal structures, see: Karthikeyan et al. (2012). For E-conformation aspects, see: Dunitz & Schweizer (1982). For resonance effects of acrylate, see: Merlino (1971); Varghese et al. (1986). For graph-set motif notation, see: Bernstein et al. (1995).

Experimental

Crystal data

• C₁₁H₁₀O₄

• M_r = 206.19

• Monoclinic, P 2₁ /c

• a = 17.7458 (8) Å

• b = 4.0629 (2) Å

• c = 14.5745 (7) Å

• β = 107.868 (3)°

• V = 1000.13 (8) ų

• Z = 4

• Mo Kα radiation

• μ = 0.11 mm⁻¹

• T = 293 K

• 0.20 × 0.15 × 0.10 mm

Data collection

• Bruker SMART APEXII CCD diffractometer

• 13052 measured reflections

• 2015 independent reflections

• 1523 reflections with I > 2σ(I)

• R_int = 0.027

Refinement

• R[F² > 2σ(F²)] = 0.045

• wR(F²) = 0.155

• S = 1.06

• 2015 reflections

• 137 parameters

• H-atom parameters constrained

• Δρ_max = 0.23 e Å⁻³

• Δρ_min = −0.17 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C9—H9⋯O2^i	0.93	2.54	3.440 (2)	164
C8—H8⋯O4^ii	0.93	2.61	3.529 (2)	171
C11—H11C⋯O2^iii	0.96	2.63	3.578 (2)	168
Symmetry codes: (i) -x+1, -y+2, -z+2; (ii) ; (iii) .

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009).

Supporting information

S1. Comment

Cinnamic acid derivatives have received attention in medicinal research as traditional as well as recent synthetic antitumor agents (De et al., 2011). They also posses significant antibacterial activities against staphylococcus aureus (Xiao et al., 2008). Different substitutions on the basic moiety lead to various pharmacological activities, such as antioxidant, hepatoprotective, anxiolytic, insect repellent, antidiabetic, and anticholesterolemic (Sharma, 2011).

In the title molecule, Fig. 1, the methyl acrylate group is essentially planar, with a maximum deviation of 0.0264 (19) Å for atom C9. Its mean plane forms a dihedral angle of 31.74 (6)° with the benzene ring (C2—C7). The molecular dimensions are in excellent agreement with the those reported for a closely related compound (Karthikeyan et al., 2012).

The configuration of the keto group with respect to the olefinic double bond is typically S-trans, with the O2═C10—C9═C8 torsion angle = 178.78 (19)°. The methyl acrylate group adopts an extended E conformation with torsion angles C8═C9—C10═O2 = 178.78 (19)°, C8═ C9—C10—O1 = -1.2 (3)°, C9—C10—O1—C11 = -178.82 (16)° and O2═ C10—O1—C11 = 1.2 (3)°. The extended conformation is supported by the fact that the bond angles involving carbonyl O atoms are invariably enlarged (Dunitz & Schweizer, 1982).

The significant difference in the bond lengths C10—O1 = 1.342 (2) Å and C11—O1 = 1.438 (2) Å is attributed to a partial contribution from the O^-—C═O⁺—C resonance structure of the O2═C10—O1—C11 group (Merlino, 1971). This feature, commonly observed for the carboxylic ester group of substituents in various compounds gives average values of 1.340 Å and 1.447 Å, respectively (Varghese et al., 1986).

The crystal packing (Fig. 2 and Table 1) is stabilized by C—H···O intermolecular interactions. The molecules are linked into inversion dimers via C9—H9···O2 interactions resulting in an R²₂(8) graph-set motif (Bernstein et al., 1995). The dimers are further consolidated by R²₃(16) graph-set ring motifs via C8—H8···O4 and C11—H11C···O2 interactions resulting in chains of molecules running parallel to the c axis; the keto group O atom (O2) is involved in bifurcated hydrogen bonding.

Related literature

For applications of acrylate derivatives, see: Xiao et al. (2008); De et al. (2011); Sharma (2011). For related crystal structures, see: Karthikeyan et al. (2012). For E-conformation aspects, see: Dunitz & Schweizer (1982). For resonance effects of acrylate, see: Merlino (1971); Varghese et al. (1986). For graph-set motif notation, see: Bernstein et al. (1995).

S2. Experimental

Salicylaldehyde (1 mmol) was dissolved in an aqueous solution of K₂CO₃ (1 mmol) and methyl propiolate (1 mmol) was added. The reaction mixture was stirred vigorously at room temperature. A turbid solution was formed by consumption of salicylaldehyde (monitored by TLC) in 5 min, the reaction mixture then became clear. The title compound was precipitated as a solid in water. The product was isolated by filtration without further purification [Yield 75%]. Block-like colourless crystals were obtained by slow evaporation of a solution in ethylacetate.

S3. Refinement

The H atoms could all be located in difference electron-density maps. In the final cycles of refinement they were treated as riding atoms: C—H = 0.93 and 0.96 Å for CH and CH₃ H atoms, respectively, with U_iso(H) = 1.5 U_eq(C– methyl) and = 1.2U_eq(C) for other H atoms.

Computing details

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and Mercury (Macrae et al.,2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures

	Fig. 1. The molecular structure of the title molecule, with atom labelling. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. The crystal packing of the title compound viewed along the b axis, showing the formation of the R^22(8) graph-set motif. The dimers are further consolidated by R^23(16) graph-set ring motifs. Hydrogen bonds are shown as dashed lines (see Table 1 for details; H atoms not involved in these interactions have been omitted for clarity).)

Methyl (E)-3-(2-formylphenoxy)acrylate

Crystal data

C11H10O4	F(000) = 432
Mr = 206.19	Dx = 1.369 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -p 2ybc	Cell parameters from 2015 reflections
a = 17.7458 (8) Å	θ = 1.2–26.3°
b = 4.0629 (2) Å	µ = 0.11 mm^−1
c = 14.5745 (7) Å	T = 293 K
β = 107.868 (3)°	Block, colorless
V = 1000.13 (8) Å^3	0.20 × 0.15 × 0.10 mm
Z = 4

Data collection

Bruker SMART APEXII CCD diffractometer	1523 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.027
Graphite monochromator	θmax = 26.3°, θmin = 1.2°
ω scans	h = −22→21
13052 measured reflections	k = −5→5
2015 independent reflections	l = −18→18

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.155	H-atom parameters constrained
S = 1.06	w = 1/[σ^2(Fo^2) + (0.1001P)^2 + 0.0957P] where P = (Fo^2 + 2Fc^2)/3
2015 reflections	(Δ/σ)max < 0.001
137 parameters	Δρmax = 0.23 e Å^−3
0 restraints	Δρmin = −0.17 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
C1	0.19462 (11)	0.6483 (5)	1.09554 (11)	0.0570 (5)
H1	0.2426	0.7588	1.1079	0.068*
C2	0.16126 (8)	0.4928 (4)	1.00055 (10)	0.0437 (4)
C3	0.08802 (9)	0.3378 (4)	0.97865 (12)	0.0518 (5)
H3	0.0621	0.3250	1.0252	0.062*
C4	0.05341 (10)	0.2034 (5)	0.88901 (13)	0.0574 (5)
H4	0.0040	0.1033	0.8746	0.069*
C5	0.09250 (10)	0.2182 (5)	0.82056 (12)	0.0545 (5)
H5	0.0692	0.1265	0.7600	0.065*
C6	0.16554 (9)	0.3671 (4)	0.84083 (11)	0.0484 (4)
H6	0.1918	0.3734	0.7946	0.058*
C7	0.19943 (8)	0.5068 (4)	0.93033 (10)	0.0425 (4)
C8	0.30241 (9)	0.7868 (4)	0.88985 (11)	0.0463 (4)
H8	0.2706	0.8014	0.8260	0.056*
C9	0.37579 (9)	0.8937 (5)	0.91462 (12)	0.0542 (5)
H9	0.4075	0.8649	0.9780	0.065*
C10	0.40974 (9)	1.0549 (5)	0.84737 (12)	0.0516 (4)
C11	0.39059 (12)	1.2299 (6)	0.68764 (14)	0.0655 (5)
H11A	0.4103	1.4452	0.7097	0.098*
H11B	0.3494	1.2484	0.6272	0.098*
H11C	0.4329	1.0976	0.6794	0.098*
O1	0.35946 (7)	1.0781 (3)	0.75754 (8)	0.0598 (4)
O2	0.47632 (7)	1.1596 (4)	0.86851 (10)	0.0723 (5)
O3	0.27287 (6)	0.6544 (3)	0.95771 (7)	0.0541 (4)
O4	0.16367 (9)	0.6413 (5)	1.15808 (9)	0.0821 (5)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0536 (10)	0.0738 (13)	0.0448 (8)	0.0075 (8)	0.0171 (7)	0.0039 (8)
C2	0.0403 (8)	0.0498 (10)	0.0419 (8)	0.0095 (6)	0.0142 (6)	0.0084 (7)
C3	0.0432 (9)	0.0604 (11)	0.0562 (9)	0.0071 (7)	0.0220 (7)	0.0119 (8)
C4	0.0442 (9)	0.0590 (11)	0.0665 (11)	−0.0046 (8)	0.0134 (8)	0.0077 (8)
C5	0.0531 (10)	0.0542 (10)	0.0504 (9)	0.0009 (8)	0.0074 (7)	0.0007 (8)
C6	0.0485 (9)	0.0547 (10)	0.0443 (8)	0.0048 (7)	0.0175 (7)	0.0049 (7)
C7	0.0357 (7)	0.0485 (10)	0.0429 (7)	0.0054 (6)	0.0115 (6)	0.0082 (6)
C8	0.0411 (8)	0.0565 (10)	0.0435 (8)	0.0025 (7)	0.0162 (6)	0.0013 (7)
C9	0.0425 (8)	0.0710 (12)	0.0490 (9)	−0.0019 (8)	0.0137 (7)	−0.0027 (8)
C10	0.0383 (8)	0.0609 (11)	0.0580 (9)	−0.0018 (7)	0.0184 (7)	−0.0063 (8)
C11	0.0639 (11)	0.0721 (13)	0.0669 (11)	−0.0039 (10)	0.0297 (9)	0.0095 (10)
O1	0.0487 (7)	0.0767 (9)	0.0553 (7)	−0.0123 (6)	0.0181 (5)	0.0033 (6)
O2	0.0431 (7)	0.1021 (13)	0.0731 (8)	−0.0180 (7)	0.0197 (6)	−0.0050 (7)
O3	0.0403 (6)	0.0800 (9)	0.0427 (6)	−0.0071 (5)	0.0139 (5)	0.0042 (5)
O4	0.0787 (10)	0.1250 (15)	0.0509 (7)	−0.0008 (9)	0.0322 (7)	−0.0084 (7)

Geometric parameters (Å, º)

C1—O4	1.200 (2)	C7—O3	1.3778 (18)
C1—C2	1.471 (2)	C8—C9	1.314 (2)
C1—H1	0.9300	C8—O3	1.3640 (18)
C2—C3	1.390 (2)	C8—H8	0.9300
C2—C7	1.3910 (19)	C9—C10	1.454 (2)
C3—C4	1.375 (3)	C9—H9	0.9300
C3—H3	0.9300	C10—O2	1.2035 (19)
C4—C5	1.380 (2)	C10—O1	1.342 (2)
C4—H4	0.9300	C11—O1	1.438 (2)
C5—C6	1.378 (2)	C11—H11A	0.9600
C5—H5	0.9300	C11—H11B	0.9600
C6—C7	1.380 (2)	C11—H11C	0.9600
C6—H6	0.9300
O4—C1—C2	123.98 (17)	O3—C7—C2	115.83 (13)
O4—C1—H1	118.0	C6—C7—C2	120.61 (14)
C2—C1—H1	118.0	C9—C8—O3	120.00 (14)
C3—C2—C7	118.80 (14)	C9—C8—H8	120.0
C3—C2—C1	119.24 (14)	O3—C8—H8	120.0
C7—C2—C1	121.91 (15)	C8—C9—C10	122.98 (15)
C4—C3—C2	120.77 (15)	C8—C9—H9	118.5
C4—C3—H3	119.6	C10—C9—H9	118.5
C2—C3—H3	119.6	O2—C10—O1	122.10 (15)
C3—C4—C5	119.52 (16)	O2—C10—C9	124.32 (16)
C3—C4—H4	120.2	O1—C10—C9	113.58 (14)
C5—C4—H4	120.2	O1—C11—H11A	109.5
C6—C5—C4	120.83 (15)	O1—C11—H11B	109.5
C6—C5—H5	119.6	H11A—C11—H11B	109.5
C4—C5—H5	119.6	O1—C11—H11C	109.5
C5—C6—C7	119.46 (15)	H11A—C11—H11C	109.5
C5—C6—H6	120.3	H11B—C11—H11C	109.5
C7—C6—H6	120.3	C10—O1—C11	115.85 (13)
O3—C7—C6	123.51 (13)	C8—O3—C7	120.10 (12)
O4—C1—C2—C3	2.7 (3)	C3—C2—C7—C6	−0.5 (2)
O4—C1—C2—C7	−179.85 (17)	C1—C2—C7—C6	−178.03 (15)
C7—C2—C3—C4	−0.6 (2)	O3—C8—C9—C10	−176.28 (16)
C1—C2—C3—C4	176.94 (17)	C8—C9—C10—O2	178.78 (19)
C2—C3—C4—C5	1.0 (3)	C8—C9—C10—O1	−1.2 (3)
C3—C4—C5—C6	−0.3 (3)	O2—C10—O1—C11	1.2 (3)
C4—C5—C6—C7	−0.9 (3)	C9—C10—O1—C11	−178.82 (16)
C5—C6—C7—O3	178.55 (15)	C9—C8—O3—C7	−172.25 (16)
C5—C6—C7—C2	1.3 (2)	C6—C7—O3—C8	26.2 (2)
C3—C2—C7—O3	−178.02 (14)	C2—C7—O3—C8	−156.37 (14)
C1—C2—C7—O3	4.5 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9···O2^i	0.93	2.54	3.440 (2)	164
C8—H8···O4^ii	0.93	2.61	3.529 (2)	171
C11—H11C···O2^iii	0.96	2.63	3.578 (2)	168

Symmetry codes: (i) −x+1, −y+2, −z+2; (ii) x, −y+3/2, z−1/2; (iii) −x+1, y−1/2, −z+3/2.