(E)-Methyl 3-(3,4-dihy­droxy­phen­yl)acrylate

Wang, L.; Meng, F.-Y.; Lin, C.-W.; Chen, H.-Y.; Luo, X.

doi:10.1107/S1600536810054504

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 67| Part 2| February 2011| Page o354

doi:10.1107/S1600536810054504

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(E)-Methyl 3-(3,4-dihydroxyphenyl)acrylate

Li Wang,^a Fa-Yan Meng,^a Cui-Wu Lin,^a ^* Hai-Yan Chen ^a and Xuan Luo ^a

^aCollege of Chemistry and Chemical Engineering, Guangxi University, Guangxi 530004, People's Republic of China
^*Correspondence e-mail: cuiwulin@yahoo.com.cn

(Received 21 October 2010; accepted 28 December 2010; online 12 January 2011)

The benzene ring in the title compound, C₁₀H₁₀O₄, makes an angle of 4.4 (1)° with the C—C—C—O linker. The hydroxy groups are involved in both intra- and intermolecular O—H⋯O hydrogen bonds. The crystal packing is stabilized by O—H⋯O hydrogen-bonding interactions. The molecules of the caffeic acid ester form a dimeric structure in a head-to-head manner along the a axis through O—H⋯O hydrogen bonds. The dimers interact with one another through O—H⋯O hydrogen bonds, forming supermolecular chains. These chains are further extended through C—H⋯O hydrogen bonds as well as van der Waals interactions into the final three-dimensional architecture.

Related literature

For properties of caffeic acids and their esters, see: Altug et al. (2008 ); Ates et al. (2006 ); Atik et al. (2006 ); Chun et al. (2008 ); Huang et al. (2010 ); Hwang et al. (2001 ); Padinchare et al. (2001 ). For a polymorphic form of the title compound, see: Chen et al. (1979 ).

Experimental

Crystal data

C₁₀H₁₀O₄
M_r = 194.18
Triclinic, $[P \overline 1]$
a = 5.129 (5) Å
b = 9.969 (8) Å
c = 10.586 (9) Å
α = 117.627 (7)°
β = 97.924 (11)°
γ = 94.322 (11)°
V = 468.9 (7) Å³
Z = 2
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 296 K
0.33 × 0.24 × 0.18 mm

Data collection

Multiwire proportional diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.966, T_max = 0.981
2494 measured reflections
1619 independent reflections
1337 reflections with I > 2σ(I)
R_int = 0.013

Refinement

R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.120
S = 1.05
1619 reflections
128 parameters
H-atom parameters constrained
Δρ_max = 0.18 e Å⁻³
Δρ_min = −0.13 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4—H4A⋯O3	0.82	2.28	2.723 (2)	114
O4—H4A⋯O3ⁱ	0.82	2.15	2.835 (2)	141
O3—H3A⋯O2ⁱⁱ	0.82	1.95	2.764 (2)	175
C10—H10A⋯O2ⁱⁱ	0.93	2.56	3.260 (4)	132
Symmetry codes: (i) -x, -y, -z+1; (ii) -x+1, -y, -z.

Data collection: SMART (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT; 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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810054504/bg2376sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810054504/bg2376Isup2.hkl

checkCIF report

Comment top

Some naturally occurring caffeic acids and their esters attract much attention in biology and medicine (Hwang et al., 2001; Altug et al., 2008). These compounds show antiviral, antibacterial, vasoactive, antiatherogenic, antiproliferative, antioxidant and antiinflammatory properties (Atik et al., 2006; Padinchare et al., 2001; Ates et al., 2006). Our previous research found that the phenolic acids compounds including caffeic acid, chlorogenic acid, ferulic acid, vanillic acid, syringic acid and protocatechuic acid from Blumea riparia DC have a significant role at antiplatelet activity (Huang et al.., 2010). This prompted us to synthesize a series of caffeic acid esters and amides to investigate their properties. In this paper, we report a polymorph of C₁₀H₁₀O₄ (Chen et al.., 1979).

In the title compound (Fig. 1), all values of the geometric parameters are normal. The benzene ring is planar within experimental error and it makes an angle of 4.4 (1)° to the linker (C2–C3–C4–O2). Hydroxy groups contribute to intermolecular O—H···O hydrogen bonds. In the case of caffeic esters, the presence of an ethylenic spacer allows the formation of a conjugated system, strongly stabilized through π-electron delocalization (Chun et al., 2008).

The bond C3=C4 is a trans-double bond. The crystal packing is stabilized by intramolecular (Table 1, entries 1 and 2) and intermolecular hydrogen-bonding interactions (Table 1, remaining entries). The molecules of the caffeic acid ester form a dimeric structure through O—H···O hydrogen bonds along the a axis in a head-to-head manner (Table 1, third entry) . The dimer interacts with another dimmer through O—H···O hydrogen bonds (Table 1, fourth entry) to form one-dimensional supermolecule chains. These one-dimensional supermolecule chains are further extended through C—H···O hydrogen bonds (Table 1, fifth entry) as well as van der Waals interactions into the final 3-D architecture (Fig.2).

Related literature top

For properties of caffeic acids and their esters, see: Altug et al. (2008); Ates et al. (2006); Atik et al. (2006); Chun et al. (2008); Huang et al. (2010); Hwang et al. (2001); Padinchare et al. (2001). For a polymorphic form of the title compound, see: Chen et al. (1979)

Experimental top

Commercial caffeic acid (1.79 g, 10 mmol) was dissolved in tetrahydrofuran solution(16 ml), followed by methanol (16 ml) and the addition of concentrated hydrochloric acid (8 ml). The mixture was stirred at 60 °C for 60 minutes, followed by the addition of water and extracted with ethyl acetate. The organic layer was washed with sodium bicarbonate and water, dried over magnesium sulfate, and concentrated to give a solid residue. The residue was recrystallized from petroleum ether to give the title compound as a colourless crystal (1.64 g, yield: 84%)

Computing details top

Data collection: SMART (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); 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

	Fig. 1. View of the molecular structure of (E)-methyl 3-(3,4-dihydroxyphenyl)acrylate with displacement ellipsoids at a 45% probability level. Dashed lines represent intramolecular hydrogen bonds.
	Fig. 2. Packing of the molecules drawn along the b axis. Dashed lines represent hydrogen bonds.

(E)-Methyl 3-(3,4-dihydroxyphenyl)acrylate top

Crystal data top

C₁₀H₁₀O₄	Z = 2
M_r = 194.18	F(000) = 204
Triclinic, P1	D_x = 1.375 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 5.129 (5) Å	Cell parameters from 1619 reflections
b = 9.969 (8) Å	θ = 2.2–25.0°
c = 10.586 (9) Å	µ = 0.11 mm⁻¹
α = 117.627 (7)°	T = 296 K
β = 97.924 (11)°	Block, colourless
γ = 94.322 (11)°	0.33 × 0.24 × 0.18 mm
V = 468.9 (7) Å³

Data collection top

Multiwire proportional diffractometer	1619 independent reflections
Radiation source: fine-focus sealed tube	1337 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.013
phi and ω scans	θ_max = 25.0°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −6→5
T_min = 0.966, T_max = 0.981	k = −11→11
2494 measured reflections	l = −12→11

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)] = 0.040	H-atom parameters constrained
wR(F²) = 0.120	w = 1/[σ²(F_o²) + (0.0615P)² + 0.0896P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max < 0.001
1619 reflections	Δρ_max = 0.18 e Å⁻³
128 parameters	Δρ_min = −0.13 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.023 (7)

Crystal data top

C₁₀H₁₀O₄	γ = 94.322 (11)°
M_r = 194.18	V = 468.9 (7) Å³
Triclinic, P1	Z = 2
a = 5.129 (5) Å	Mo Kα radiation
b = 9.969 (8) Å	µ = 0.11 mm⁻¹
c = 10.586 (9) Å	T = 296 K
α = 117.627 (7)°	0.33 × 0.24 × 0.18 mm
β = 97.924 (11)°

Data collection top

Multiwire proportional diffractometer	1619 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	1337 reflections with I > 2σ(I)
T_min = 0.966, T_max = 0.981	R_int = 0.013
2494 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	0 restraints
wR(F²) = 0.120	H-atom parameters constrained
S = 1.05	Δρ_max = 0.18 e Å⁻³
1619 reflections	Δρ_min = −0.13 e Å⁻³
128 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

	x	y	z	U_iso*/U_eq
O1	0.3038 (3)	0.37534 (14)	−0.18804 (13)	0.0565 (4)
O2	0.5270 (3)	0.19675 (16)	−0.17913 (15)	0.0718 (5)
O3	0.1400 (2)	−0.02223 (14)	0.35179 (13)	0.0548 (4)
H3A	0.2389	−0.0773	0.3036	0.082*
O4	−0.2041 (3)	0.17229 (17)	0.47736 (15)	0.0696 (5)
H4A	−0.1537	0.1033	0.4914	0.104*
C1	0.4334 (5)	0.3652 (2)	−0.3048 (2)	0.0689 (6)
H1A	0.3752	0.4367	−0.3354	0.103*
H1B	0.3878	0.2631	−0.3853	0.103*
H1C	0.6232	0.3891	−0.2711	0.103*
C2	0.3676 (3)	0.28238 (18)	−0.13522 (17)	0.0436 (4)
C3	0.2244 (3)	0.29584 (18)	−0.02085 (17)	0.0445 (4)
H3B	0.1053	0.3654	0.0075	0.053*
C4	0.2628 (3)	0.20962 (19)	0.04297 (18)	0.0460 (4)
H4B	0.3849	0.1428	0.0100	0.055*
C5	0.1401 (3)	0.20498 (18)	0.15770 (17)	0.0424 (4)
C6	−0.0350 (3)	0.30272 (19)	0.22626 (19)	0.0513 (5)
H6A	−0.0774	0.3767	0.2001	0.062*
C7	−0.1459 (4)	0.2904 (2)	0.3326 (2)	0.0568 (5)
H7A	−0.2618	0.3568	0.3778	0.068*
C8	−0.0874 (3)	0.1811 (2)	0.37298 (18)	0.0476 (4)
C9	0.0889 (3)	0.08337 (18)	0.30649 (16)	0.0423 (4)
C10	0.2006 (3)	0.09637 (18)	0.20077 (17)	0.0442 (4)
H10A	0.3192	0.0312	0.1571	0.053*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0832 (9)	0.0569 (7)	0.0553 (7)	0.0308 (6)	0.0364 (6)	0.0392 (6)
O2	0.0865 (10)	0.0896 (10)	0.0850 (10)	0.0535 (8)	0.0538 (8)	0.0637 (8)
O3	0.0709 (8)	0.0646 (8)	0.0599 (7)	0.0330 (6)	0.0364 (6)	0.0458 (6)
O4	0.0859 (10)	0.0920 (10)	0.0775 (9)	0.0488 (8)	0.0561 (8)	0.0633 (8)
C1	0.1062 (17)	0.0689 (12)	0.0585 (11)	0.0311 (11)	0.0432 (11)	0.0430 (10)
C2	0.0502 (10)	0.0428 (8)	0.0462 (9)	0.0123 (7)	0.0160 (7)	0.0257 (7)
C3	0.0501 (10)	0.0474 (9)	0.0464 (9)	0.0156 (7)	0.0185 (7)	0.0275 (7)
C4	0.0511 (10)	0.0498 (9)	0.0487 (9)	0.0161 (7)	0.0205 (8)	0.0291 (8)
C5	0.0451 (9)	0.0463 (9)	0.0438 (8)	0.0104 (7)	0.0143 (7)	0.0263 (7)
C6	0.0596 (11)	0.0559 (10)	0.0588 (10)	0.0233 (8)	0.0246 (8)	0.0388 (9)
C7	0.0644 (12)	0.0650 (11)	0.0655 (11)	0.0341 (9)	0.0361 (9)	0.0418 (10)
C8	0.0520 (10)	0.0588 (10)	0.0467 (9)	0.0178 (8)	0.0233 (7)	0.0324 (8)
C9	0.0470 (9)	0.0475 (9)	0.0424 (8)	0.0121 (7)	0.0142 (7)	0.0278 (7)
C10	0.0490 (10)	0.0486 (9)	0.0456 (9)	0.0173 (7)	0.0209 (7)	0.0268 (7)

Geometric parameters (Å, º) top

O1—C2	1.325 (2)	C3—H3B	0.9300
O1—C1	1.449 (2)	C4—C5	1.460 (2)
O2—C2	1.206 (2)	C4—H4B	0.9300
O3—C9	1.372 (2)	C5—C6	1.392 (2)
O3—H3A	0.8200	C5—C10	1.395 (2)
O4—C8	1.361 (2)	C6—C7	1.378 (2)
O4—H4A	0.8200	C6—H6A	0.9300
C1—H1A	0.9600	C7—C8	1.381 (2)
C1—H1B	0.9600	C7—H7A	0.9300
C1—H1C	0.9600	C8—C9	1.391 (2)
C2—C3	1.460 (2)	C9—C10	1.378 (2)
C3—C4	1.327 (2)	C10—H10A	0.9300

C2—O1—C1	115.65 (14)	C6—C5—C10	118.11 (15)
C9—O3—H3A	109.5	C6—C5—C4	123.59 (15)
C8—O4—H4A	109.5	C10—C5—C4	118.30 (14)
O1—C1—H1A	109.5	C7—C6—C5	120.39 (15)
O1—C1—H1B	109.5	C7—C6—H6A	119.8
H1A—C1—H1B	109.5	C5—C6—H6A	119.8
O1—C1—H1C	109.5	C6—C7—C8	121.02 (16)
H1A—C1—H1C	109.5	C6—C7—H7A	119.5
H1B—C1—H1C	109.5	C8—C7—H7A	119.5
O2—C2—O1	122.42 (15)	O4—C8—C7	118.86 (15)
O2—C2—C3	124.94 (14)	O4—C8—C9	121.79 (15)
O1—C2—C3	112.64 (14)	C7—C8—C9	119.35 (15)
C4—C3—C2	120.52 (15)	O3—C9—C10	123.84 (14)
C4—C3—H3B	119.7	O3—C9—C8	116.62 (14)
C2—C3—H3B	119.7	C10—C9—C8	119.54 (14)
C3—C4—C5	129.05 (16)	C9—C10—C5	121.59 (14)
C3—C4—H4B	115.5	C9—C10—H10A	119.2
C5—C4—H4B	115.5	C5—C10—H10A	119.2

C1—O1—C2—O2	1.4 (3)	C6—C7—C8—O4	−179.27 (17)
C1—O1—C2—C3	−178.44 (15)	C6—C7—C8—C9	0.9 (3)
O2—C2—C3—C4	−0.5 (3)	O4—C8—C9—O3	−0.2 (2)
O1—C2—C3—C4	179.32 (15)	C7—C8—C9—O3	179.66 (16)
C2—C3—C4—C5	−179.72 (15)	O4—C8—C9—C10	179.64 (16)
C3—C4—C5—C6	−3.9 (3)	C7—C8—C9—C10	−0.5 (3)
C3—C4—C5—C10	175.86 (16)	O3—C9—C10—C5	179.43 (14)
C10—C5—C6—C7	−0.6 (3)	C8—C9—C10—C5	−0.4 (3)
C4—C5—C6—C7	179.19 (17)	C6—C5—C10—C9	0.9 (2)
C5—C6—C7—C8	−0.3 (3)	C4—C5—C10—C9	−178.84 (15)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4A···O3	0.82	2.28	2.723 (2)	114
C4—H4B···O2	0.93	2.48	2.829 (4)	102
O4—H4A···O3ⁱ	0.82	2.15	2.835 (2)	141
O3—H3A···O2ⁱⁱ	0.82	1.95	2.764 (2)	175
C10—H10A···O2ⁱⁱ	0.93	2.56	3.260 (4)	132

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

Experimental details

Crystal data
Chemical formula	C₁₀H₁₀O₄
M_r	194.18
Crystal system, space group	Triclinic, P1
Temperature (K)	296
a, b, c (Å)	5.129 (5), 9.969 (8), 10.586 (9)
α, β, γ (°)	117.627 (7), 97.924 (11), 94.322 (11)
V (Å³)	468.9 (7)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.33 × 0.24 × 0.18

Data collection
Diffractometer	Multiwire proportional diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.966, 0.981
No. of measured, independent and observed [I > 2σ(I)] reflections	2494, 1619, 1337
R_int	0.013
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.120, 1.05
No. of reflections	1619
No. of parameters	128
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.18, −0.13

Computer programs: SMART (Bruker, 2005), SAINT (Bruker, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4A···O3	0.82	2.28	2.723 (2)	114.3
C4—H4B···O2	0.93	2.48	2.829 (4)	102
O4—H4A···O3ⁱ	0.82	2.15	2.835 (2)	140.6
O3—H3A···O2ⁱⁱ	0.82	1.95	2.764 (2)	174.5
C10—H10A···O2ⁱⁱ	0.93	2.56	3.260 (4)	132

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

Acknowledgements

This work was supported by a grant from the National Natural Science Foundation of China (20962002, 20662001) and the National Undergraduates Innovating Experimentation Project (091059314).

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