(E)-2-Cyano-3-(2,3-dimeth­oxy­phen­yl)acrylic acid

Aliakbar Dehno Khalaji; Karla Fejfarová; Michal Dušek

doi:10.1107/S1600536811051129

. 2011 Nov 30;67(Pt 12):o3508–o3509. doi: 10.1107/S1600536811051129

(E)-2-Cyano-3-(2,3-dimethoxyphenyl)acrylic acid

Aliakbar Dehno Khalaji ^a, Karla Fejfarová ^b,^*, Michal Dušek ^b

PMCID: PMC3239130 PMID: 22199978

Abstract

The asymmetric unit of the title compound, C₁₂H₁₁NO₄, contains two molecules. In the crystal, neighbouring molecules are linked together by O—H⋯O hydrogen bonds into dimers. The dimers are arranged into columns parallel to the a axis, meditated by π–π interactions [centroid–centroid distances = 3.856 (3) and 3.857 (3) Å]. The crystal structure is further stabilized by weak intermolecular C—H⋯O interactions. The crystal studied was a non-merohedral twin with a ratio of the twin components of 0.657 (11):0.343 (11).

Related literature

For applications of cyanoacrylic acid derivatives, see: Hagberg et al. (2006 ▶); Kim et al. (2008 ▶); Hara et al. (2003 ▶). For structures and properties of complexes based on carboxylate ligands, see, for example: Zhao et al. (2008 ▶); Wang et al. (2009 ▶); Mitra et al. (2006 ▶); Shit et al. (2009 ▶); Akhbari et al. (2009 ▶).

Experimental

Crystal data

C₁₂H₁₁NO₄
M _r = 233.2
Monoclinic,
a = 3.8564 (5) Å
b = 27.178 (3) Å
c = 10.4681 (9) Å
β = 99.966 (9)°
V = 1080.6 (2) Å³
Z = 4
Cu Kα radiation
μ = 0.92 mm⁻¹
T = 120 K
0.57 × 0.15 × 0.05 mm

Data collection

Agilent Xcalibur diffractometer with an Atlas (Gemini ultra Cu) detector
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010 ▶) T _min = 0.525, T _max = 1
17777 measured reflections
1922 independent reflections
1638 reflections with I > 3σ(I)
R _int = 0.083

Refinement

R[F ² > 3σ(F ²)] = 0.049
wR(F ²) = 0.129
S = 1.73
1922 reflections
314 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.23 e Å⁻³
Δρ_min = −0.23 e Å⁻³

Data collection: CrysAlis PRO (Agilent, 2010 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SIR2002 (Burla et al., 2003 ▶); program(s) used to refine structure: JANA2006 (Petříček et al., 2006 ▶); molecular graphics: DIAMOND (Brandenburg & Putz, 2005 ▶) and COOT (Emsley et al., 2010 ▶); software used to prepare material for publication: JANA2006.

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811051129/bt5719sup1.cif

e-67-o3508-sup1.cif^{(38.8KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811051129/bt5719Isup2.hkl

e-67-o3508-Isup2.hkl^{(75.9KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811051129/bt5719Isup3.cdx

Supplementary material file. DOI: 10.1107/S1600536811051129/bt5719Isup4.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O6—H6o⋯O1ⁱ	0.85 (5)	1.82 (6)	2.62 (3)	154 (6)
O2—H2o⋯O5ⁱⁱ	0.85 (6)	1.79 (6)	2.63 (3)	169 (8)
C11—H11c⋯O4ⁱⁱⁱ	0.96	2.56	3.50 (3)	167
C23—H23a⋯O3ⁱⁱⁱ	0.96	2.56	3.42 (4)	149

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) .

Acknowledgments

We acknowledge Golestan University and the Islamic Azad University, Qaemshahr, for partial support of this work, and the Institutional Research Plan No. AVOZ10100521 of the Institute of Physics and the Praemium Academiae Project of the Academy of Sciences of the Czech Republic.

supplementary crystallographic information

Comment

Carboxylate compounds, an important family of O-donor ligands, can coordinate to different metal ions forming versatile structures with different topologies and stabilities (Zhao et al., 2008; Wang et al., 2009). Transition metal complexes with these ligands have special properties and applications (Mitra et al., 2006; Shit et al., 2009; Akhbari et al., 2009;). Among the carboxylate compounds, cyanoacrylic acid derivatives are of great importance to convert solar light into electricity in dye-sensitized solar cells (Hagberg et al., 2006; Kim et al., 2008 and Hara et al., 2003).

In consideration of the important applications of carboxylate compounds, herein the crystal structure of the title compound, (I), is reported. Systematic characterization of (I) has been performed by elemental analyses, FT—IR, ¹H-NMR, UV-Vis spectroscopy and x-ray crystallography

The molecular structure of (I) with the atom-numbering scheme is presented in Fig. 1. The asymmetric unit of (I) contains two molecules, which differ mainly in the orientation of methoxy groups (Fig. 3) as reflected in the C1—C2—O3—C11 and C13—C14—O7—C23 torsion angles of -120.5 (7)° and 121.0 (7) °, respectively. In both molecules, the phenyl ring and the chain connecting the ring to the CN and COOH groups are nearly coplanar. The dihedral angles between the planes of the phenyl rings (C1–C6, C13–C18) and the planes defined by C7–C10 and C19–C22, are 5.7 (4)° and 5.5 (4) °, respectively. This degree of coplanarity allows for increased π-conjugation in the title compound.

Careful inspection of the packing diagram (Fig. 2) lead us to assumption that the two independent molecules could be related by non-crystallographic inversion center. To test this assumption, we used in the first step a rigid-body approach available in the crystallographic package JANA2006 (Petříček et al., 2006). The atoms of the first molecule (C1—C12, N1, O1–O4) were taken as a model molecule and refined to obtain the geometry of the model molecule. Together with the model molecule we refined a translation vector and three rotation angles transforming the model molecule to the actual position A (C1—C12, N1, O1–O4) and another translation vector and three rotation angles transforming the inverted model molecule to the actual position B (C13–C24, N2, O5–O7). The resulting R value was 5.2% for 164 refined parameters, providing evidence that the geometry of A and inverted geometry of B can be considered identical. In the second step, we graphically connected corresponding atoms in the two identical molecules A and B by lines (Fig. 4) to inspect visually position of the possible non-crystallographic inversion centre. The lines did not intersect at the same point but the obtained intersections were very close indicating that the inversion center is present only approximately. In order to quantify this finding in terms of R value we used the original structure model without rigid body (i.e. the one reported in this article) and we restricted the coordinates and ADP parameters of corresponding atoms of the two molecules by a local inversion symmetry operation located at the average position of the intersections shown in Fig. 4. Indeed, the resulting R value increased to 7.1% for 158 refined parameters.

In the crystal, the molecules form hydrogen-bonded dimers via the carboxyl groups. These dimers are connected by π-π interactions (centroid-centroid distances 3.856 (3), 3.857 (3) Å into columns parallel to the a axis (Fig. 2). The crystal structure is further stabilized by weak intermolecular C—H···O interactions.

The crystal studied was a non-merohedral twin with the ratio of the twin components of 0.657 (11):0.343 (11).

Experimental

2,3-dimethoxybenzaldehyde (0.4 mmol) and cyanoacetic acid (0.4 mmol) were dissolved in a mixture of methanol:acetonitrile (1:1 v/v, 20 ml) in the presence of piperidine (0.4 mmol). The mixture was stirred and refluxed for 1.5 h to give a clear yellow solution. The mixture was cooled and the product was allowed to crystallize by slow evaporation technique at room temperature. After 5 days, yellow precipitate of (I) was formed which was collected by filtration and dried at room temperature. Recrystallization of the yellow precipitate from acetonitrile-chloroform mixture (2:1 v/v, 30 ml) by adding acetic acid afforded yellow crystals of 2-cyano-3-(2,5-dimethoxyphenyl)acrylic acid (1). Yield: 91%. Anal. Calc. for C₁₂H₁₁NO₄: C, 61.80; H, 4.75; N, 6.01%. Found: C, 61.77; H, 4.79; N, 6.08%. FT—IR (KBr, cm^-1): 2922–3059, 2839, 2220, 1697, 1678, 1571, 1497, 1469, 1458, 1425, 1381, 1364, 1297, 1248, 1234. UV–Vis, λ_max (nm)/ε (M^-1cm^-1); 241 (9287), 310 (25074). ¹H NMR (DMSO-d₆): δ = 3.81 (s, 3H), 3.85 (s, 3H), 7.25 (t, 1H), 7.33 (dd, 1H), 7.71 (dd, 1H), 8.47 (s, 1H), 14.08 (b, 1H) p.p.m..