2-(1,3-Dioxoisoindolin-2-yl)propanoic acid

Abdul Rauf Raza; Aisha Saddiqa; M Nawaz Tahir; Muhammad Danish; Talat Majeed

doi:10.1107/S1600536809040434

. 2009 Oct 10;65(Pt 11):o2678. doi: 10.1107/S1600536809040434

2-(1,3-Dioxoisoindolin-2-yl)propanoic acid

Abdul Rauf Raza ^a, Aisha Saddiqa ^a, M Nawaz Tahir ^b,^*, Muhammad Danish ^a, Talat Majeed ^a

PMCID: PMC2970965 PMID: 21578285

Abstract

The crystal structure of the title compound, C₁₁H₉NO₄, consists of infinite one-dimensional polymeric chains due to intermolecular O—H⋯O hydrogen bonds between the carboxylate and carbonyl groups. The phthalimide ring system and the C—COO group are planar, with r.m.s. deviations of 0.0253 and 0.0067 Å, respectively, from their mean square planes and the dihedral angle between them is 66.41 (7)°. The molecules are stabilized by C=O⋯π interactions and weak intramolecular C—H⋯O hydrogen bonds.

Related literature

For the medicinal properties of isocoumarin, see: Matsuda et al. (1999 ▶). For related crystal structures, see: Li & Liang (2006 ▶); Raza et al. (2009 ▶); Wheeler et al. (2004 ▶). For the graph-set analysis of hydrogen-bond patterns in crystal structures, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C₁₁H₉NO₄
M _r = 219.19
Monoclinic,
a = 9.3056 (8) Å
b = 5.9768 (4) Å
c = 9.7583 (8) Å
β = 110.988 (3)°
V = 506.73 (7) Å³
Z = 2
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 296 K
0.30 × 0.25 × 0.23 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.968, T _max = 0.974
5705 measured reflections
1381 independent reflections
1302 reflections with I > 2σ(I)
R _int = 0.023

Refinement

R[F ² > 2σ(F ²)] = 0.030
wR(F ²) = 0.082
S = 1.06
1381 reflections
153 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.16 e Å⁻³
Δρ_min = −0.13 e Å⁻³

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); 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, 1997 ▶) and PLATON (Spek, 2009 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶) and PLATON.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809040434/si2209sup1.cif

e-65-o2678-sup1.cif^{(18.1KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809040434/si2209Isup2.hkl

e-65-o2678-Isup2.hkl^{(66.7KB, 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
O3—H3A⋯O1ⁱ	0.80 (4)	1.96 (4)	2.750 (2)	172 (4)
C9—H9⋯O2	0.96 (3)	2.48 (2)	2.899 (2)	106.6 (17)
C8—O2⋯Cg1ⁱⁱ	1.20 (1)	3.09 (1)	4.0543 (17)	138 (1)

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Symmetry codes: (i) Inline graphic ; (ii) . Cg1 is the centroid of 5-membered heterocyclic ring.

Acknowledgments

The authors acknowledge the Higher Education Commission, Islamabad, Pakistan, and Bana International, Karachi, Pakistan, for funding the purchase of the diffractometer and for technical support, respectively.

supplementary crystallographic information

Comment

Isocoumarin are important components among natural products that exhibit a broad range of biological activities including anti-microbial, anti-allergic and immunomodulatory (Matsuda et al., 1999). Isocoumarins are also useful intermediates in synthesis of many important compounds e.g., isoquinoline alkaloids. The titled compound (I, Fig. 1), is an intermediate towards the synthesis of isocoumarins. The title compound has also been prepared for complexation with various metals.

We have recently reported the crystal structure of (II) (2R)-2-(1,3-Dioxoisoindolin-2-yl)-4-(methylsulfanyl)butanoic acid (Raza et al., 2009) which contain the same isoindoline. The crystal structures of (III) DL-2-(1,3-Dioxoisoindolin-2-yl)propanoic acid (Wheeler et al., 2004), (IV) (S)-2-(1,3-Dioxoisoindolin-2-yl)propanoic acid (Li & Liang, 2006) have also been reported which are the racemate of (I).

In (I) the phthalimide ring system A (C1—C8/N1/O1/O2) and the group B (C9/C10/O3/O4) are planar with r.m.s. deviations of 0.0253 and 0.0067 Å respectively, from their mean square planes. The dihedral angle between A/B is 66.41 (7)°, whereas it is 86.7 (3)° as observed in (IV). The title compound is stabilized in the form of infinite one dimensional polymeric chains due to intermolecular H-bondings (Table 1, Fig. 2). There exist a weak intramolecular H-bondings forming S(5) ring motifs (Fig. 1) (Bernstein et al., 1995). The C==O···Cg1 [Cg1 is the centroid of five membered ring (C1/C2/C7/C8/N1)] interaction (Table 1), may also be responsible for stabilizing of the molecules.

Experimental

The (S)-alanine (1.96 g, 22 mmol) and phthallic anhydride (3.6 g, 24.3 mmol) were added to a flask with constant stirring. The temperature of oil bath was kept at 433 K. Three hours later the flask was removed from oil bath, brought to room temperature and the crystals of phthallic anhydride on the walls of the flask were removed manually. The solid crude product was purified by crystallization from ethanol:water (8:2) that yielded (70%) colorless prisms of the title compound (I).