3-(4-Methoxy­phen­yl)pent-2-ene-1,5-dioic acid

Ushati Das; Shardul B Chheda; Suhas R Pednekar; Narendra P Karambelkar; T N Guru Row

doi:10.1107/S1600536808037495

. 2008 Nov 20;64(Pt 12):o2386. doi: 10.1107/S1600536808037495

3-(4-Methoxyphenyl)pent-2-ene-1,5-dioic acid

Ushati Das ^a, Shardul B Chheda ^b, Suhas R Pednekar ^b, Narendra P Karambelkar ^c, T N Guru Row ^a,^*

PMCID: PMC2959923 PMID: 21581357

Abstract

In the title compound, C₁₂H₁₂O₅, molecules are linked into antiparallel hydrogen-bonded sheets through inversion dimers generated via two O—H⋯O hydrogen bonds. Using the R ₂ ²(8) motif as a building block, hydrogen-bonded chains of a C ₂ ²(8) superstructure are then generated.

Related literature

For 3-(4-methoxyphenyl)-2-pentene-1,5-dioic acid as a synthon in organic chemistry, see: Kon & Nanji (1933 ▶); Linstead (1941 ▶). A number of heterocycles such as pyridine-2,6-diones can be obtained from it, see: Pednekar et al. (2004 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C₁₂H₁₂O₅
M _r = 236.22
Monoclinic,
a = 5.011 (1) Å
b = 10.940 (2) Å
c = 20.438 (4) Å
β = 90.665 (3)°
V = 1120.3 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 292 (2) K
0.52 × 0.32 × 0.25 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.902, T _max = 0.973
8509 measured reflections
2190 independent reflections
2140 reflections with I > 2σ(I)
R _int = 0.021

Refinement

R[F ² > 2σ(F ²)] = 0.068
wR(F ²) = 0.150
S = 1.22
2190 reflections
157 parameters
H-atom parameters constrained
Δρ_max = 0.32 e Å⁻³
Δρ_min = −0.29 e Å⁻³

Data collection: SMART (Bruker, 2004 ▶); cell refinement: SAINT (Bruker, 2004 ▶); 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, 1999 ▶) and CAMERON (Watkin et al., 1993 ▶); software used to prepare material for publication: PLATON (Spek, 2003 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808037495/bq2105sup1.cif

e-64-o2386-sup1.cif^{(19.4KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808037495/bq2105Isup2.hkl

e-64-o2386-Isup2.hkl^{(105.5KB, hkl)}

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
O1—H1⋯O2ⁱ	0.82	1.82	2.636 (3)	178
O3—H3⋯O4ⁱⁱ	0.82	1.85	2.672 (3)	175
C4—H4A⋯O2	0.97	2.19	2.834 (3)	123

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

Acknowledgments

We thank the Department of Science and Technology, India, for use of the CCD facility setup under the IRHPA–DST program at IISc.

supplementary crystallographic information

Comment

3-(4-Methoxyphenyl)-2-pentene-1,5-dioic acid (Kon & Nanji, 1933; Linstead, 1941) acts as a synthon in organic chemistry. It is a precursor for many heterocyclic ring structures due to its inherent ability to form cyclic anhydrides. A number of heterocycles like pyridine-2,6-diones can be obtained from this dicarboxylic acid (Pednekar et al., 2004). Introduction of double bond at the α,β-position of the glutaric acid, leads to the formation of a glutaconic acid. As a consequence of this, there is a noticeable change in its reactivity. The reactivity of methylene group at γ-position is primarily responsible for the electrophilic substitutions taking places at the γ-position of 3-(4-Methoxyphenyl) -2-pentene-1,5-dioic acid.

The title compound, (I) crystallizes in the monoclinic crystal system in the centrosymmetric space group P2₁/c with Z = 4. Fig. 1 shows the asymmetric unit and the atom-numbering scheme. Selected bond lengths and torsion angles are given in Table 1.

In the asymmetric unit, compound (I) adopts the E conformation, with the =CH-COOH group in the plane of the methoxy phenyl ring (C6—C3—C2—C1 dihedral angle is 174.73°) while the –CH₂—COOH group lies nearly perpendicular to the phenyl ring (C6—C3—C4—C5 dihedral angle is 89.25 °). Within the aryl rings, the C—C bonds are in the range of 1.374 (3) to 1.395 (3) Å, which is in accordance with those found in similar structures. The C—C single bonds (1.462 (3) to 1.511 (3) Å), C—C double bond (1.339 (3) Å) and C—O double bonds (1.219 (3) Å) are within the usual range.

The molecular assembly is stabilized by extensive intermolecular O—H···O hydrogen bonding, besides intramolecular C—H···O stabilizing weak interactions (Fig. 2). O1 at (x,y,z) acts as a hydrogen-bond donor to O2 at (3 - x,2 - y,-z) to form an inversion dimer centered at (1/2,0,0) and characterized by the usual R₂²(8) motif (Bernstein et al., 1995). The inversion dimer acts as a building block and leads to propagation of hydrogen bonded chains to generate a C₂²(8) superstructure. Similarly, O3 (x,y,z) acts as a hydrogen-bond donor to O4 at (2 - x,1 - y,-z) to form an inversion dimer centered at (1,1/2,0), also characterized by the R₂²(8) motif. Furthermore, the combination of two inversion dimers nearly perpendicular to one another leads to the formation of an intermolecular hydrogen-bonded staircase with neighboring inversion dimers generated via O1—H1···O2 strong hydrogen bonds being connected by O3—H3···O4 interactions. The overall supramolecular packing shows a layered arrangement, with alternate layers mutually parallel.

Experimental

To synthesize compound (I), citric acid [0.13 mol] was warmed in conc. H₂SO₄ (98%) with constant stirring till foam disappeared to obtain acetone dicarboxylic acid. By immersing the reaction flask in an ice bath; temperature was dropped down to 0°C. Anisole [0.113 mol] was then added slowly with vigorous stirring, over a period of one hour. During the addition, temperature was maintained at 0°C. Stirring was continued for a period of 6 hrs, while maintaining the temperature between 0°C to 5°C. The reaction mixture was then poured over crushed ice with stirring. The solid obtained was then filtered and washed with water and colorless single crystals grown from hot water (yield 12%, m.p. 445–447 K). ¹H NMR (DMSO):δ 12.284 (s, 2H), 7.489 (d, 2H), 6.951 (d, 2H), 6.173 (s, 1H), 4.103 (s, 2H), 3.768 (s, 3H).