(E)-Methyl 3-(3,4-dimeth­oxy­phen­yl)-2-[(1,3-dioxoisoindolin-2-yl)meth­yl]acrylate

D Kannan; M Bakthadoss; D Lakshmanan; S Murugavel

doi:10.1107/S1600536812010975

. 2012 Mar 17;68(Pt 4):o1107. doi: 10.1107/S1600536812010975

(E)-Methyl 3-(3,4-dimethoxyphenyl)-2-[(1,3-dioxoisoindolin-2-yl)methyl]acrylate

D Kannan ^a, M Bakthadoss ^a,^‡, D Lakshmanan ^b, S Murugavel ^c,^*

PMCID: PMC3344056 PMID: 22589965

Abstract

In the title compound, C₂₁H₁₉NO₆, the isoindole ring system is essentially planar [maximum deviation = 0.019 (2) Å for the N atom] and is oriented at a dihedral angle of 51.3 (1)° with respect to the benzene ring. The two methoxy groups are almost coplanar with the attached benzene ring [C—O—C—C = 3.7 (4) and 4.3 (4)°]. The molecular conformation is stabilized by an intramolecular C—H⋯O hydrogen bond, which generates an S(9) ring motif. In the crystal, molecules are linked through bifurcated C—H⋯(O,O) hydrogen bonds having R ₁ ²(5) ring motifs, forming chains along the b-axis direction. The crystal packing is further stabilzed by π–π interactions [centriod–centroid distance = 3.463 (1) Å].

Related literature

For background to the applications of isoindolins, see: Pendrak et al. (1994 ▶); De Clerck (1995 ▶); Stowers (1996 ▶); Heaney & Shuhaibar (1995 ▶). For related structures, see: Liu et al. (2004 ▶); Liang & Li (2006 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C₂₁H₁₉NO₆
M _r = 381.37
Monoclinic,
a = 15.0613 (8) Å
b = 7.6334 (4) Å
c = 16.6354 (8) Å
β = 93.522 (2)°
V = 1908.94 (17) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 293 K
0.25 × 0.23 × 0.17 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.976, T _max = 0.983
21209 measured reflections
5063 independent reflections
3241 reflections with I > 2σ(I)
R _int = 0.036

Refinement

R[F ² > 2σ(F ²)] = 0.055
wR(F ²) = 0.197
S = 1.06
5063 reflections
257 parameters
H-atom parameters constrained
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.17 e Å⁻³

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: APEX2 and SAINT (Bruker, 2004 ▶); data reduction: SAINT and XPREP (Bruker, 2004 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812010975/bt5842sup1.cif

e-68-o1107-sup1.cif^{(28.1KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812010975/bt5842Isup2.hkl

e-68-o1107-Isup2.hkl^{(243KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812010975/bt5842Isup3.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
C15—H15⋯O1	0.93	2.55	3.440 (3)	160
C4—H4⋯O5ⁱ	0.93	2.50	3.354 (3)	153
C4—H4⋯O6ⁱ	0.93	2.58	3.320 (4)	137

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Symmetry code: (i) Inline graphic .

Acknowledgments

The authors thank Dr Babu Vargheese, SAIF, IIT, Madras, India, for his help with the data collection.

supplementary crystallographic information

Comment

Isoindolinones and their derivatives have been investigated widely due to their physiological and chemotherapeutic properties. Many compounds containing the isoindolinone skeleton have shown antiviral, antileukemic, antiinflammatory, antipsychotic and antiulcer properties (Pendrak et al., 1994; De Clerck, 1995). Isoindolinones are useful for the synthesis of various drugs and naturally occurring compounds (Stowers, 1996; Heaney & Shuhaibar, 1995). In view of this biological importance, the crystal structure of the title compound has been determined and the results are presented here.

Fig. 1. shows a displacement ellipsoid plot of (I), with the atom numbering scheme. The isoindole ring system is essentially planar [maximum deviation = 0.019 (2) Å for the N1 atom] and is oriented at a dihedral angle of 51.3 (1)° with respect to the benzene ring. The methyl acrylate (O3/O4/C10–C14) plane forms dihedral angles of 83.2 (1)° and 43.7 (1)°, respectively, with the isoindole and benzene rings. The two methoxy groups at C18 and C17 are almost coplanar with the attached benzene ring as evidenced by torsion angles of C21–O6–C18–C19 = 3.7 (4) and C20–O5–C17–C16 = 4.3 (4)°, respectively. The sum of bond angles around N1 (359.9°) indicates that N1 is in sp² hybridization. The keto atoms O1 and O2 deviate by 0.034 (2) and -0.004 (2) Å, respectively, from the isoindole ring. The geometric parameters of the title molecule agrees well with those reported for similar structures (Liu et al., 2004, Liang & Li 2006).

The molecular structure is stabilized by C15—H15···O1 intramolecular hydrogen bond, forming S(9) ring motif (Bernstein et al., 1995) (Table 1). In the crystal, the molecules are linked by intermolecular C4—H4···O5ⁱ and C4—H4···O6ⁱ hydrogen bonds (Table 1; Symmetry code: (i) = 1 + x, y, z)) generating a bifurcated R₁²(5) ring motif, resulting in an extended one dimensional chains along the b axis (Fig. 2). The crystal packing is further stabilized by π—π interactions with centroid—centroid distances: Cg1—Cg2ⁱⁱⁱ = 3.463 (1) Å and Cg2—Cg1^iv = 3.463 (1) Å (Fig. 3; Cg1 and Cg2 are the centroids of N1/C1/C2/C7/C8 indole ring and C14–C19 benzene ring, respectively, symmetry code as in Fig. 3).

Experimental

A solution of 2,3-dihydro-1H-isoindole-1,3-dione (1 mmol, 0.147 g) and potassiumcarbonate (1.5 mmol, 0.207 g) in acetonitrile as solvent was stirred for 15 minutes at room temperature. To this solution, methyl (2Z)-2-(bromomethyl)-3-(3,4-dimethoxyphenyl)prop-2-enoate (1 mmol, 0.315 g) was added till the addition is complete. After the completion of the reaction as indicated by TLC, acetonitrile solvent was evaporated. Ethylacetate (15 ml) and water (15 ml) were added to the crude mass. The organic layer was dried over anhydrous sodium sulfate. Removal of solvent led to the crude product, which was purified through pad of silica gel (100–200 mesh) using ethylacetate and hexanes (1:9) as solvents. The pure title compound was obtained as a colorless solid (0.375 g, 98% yield). Recrystallization was carried out using ethylacetate as solvent.