1′-Methyl-4′-(4-methyl­phen­yl)dispiro­[1-benzopyran-3(4H),3′-pyrrolidine-2′,3′′-indoline]-2,2′′-dione

D Lakshmanan; S Murugavel; D Kannan; M Bakthadoss

doi:10.1107/S1600536811051440

. 2011 Dec 3;68(Pt 1):o11. doi: 10.1107/S1600536811051440

1′-Methyl-4′-(4-methylphenyl)dispiro[1-benzopyran-3(4H),3′-pyrrolidine-2′,3′′-indoline]-2,2′′-dione

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

PMCID: PMC3254352 PMID: 22259396

Abstract

In the title compound, C₂₇H₂₄N₂O₃, the pyrroldine ring adopts a twist conformation, while the six-membered pyranone ring of the coumarin ring system is in a sofa conformation. In the crystal, pairs of N—H⋯O hydrogen bonds link the molecules into inversion R ₂ ²(8) dimers. These dimers are further connected via C—H⋯O hydrogen bonds.

Related literature

For applications of pyrrolidine derivatives, see: Huryn et al. (1991 ▶); Suzuki et al. (1994 ▶); Waldmann (1995 ▶). For ring puckering parameters, see: Cremer & Pople (1975 ▶) and for asymmetry parameters, see: Duax et al. (1976 ▶). For closely related pyrrolidine structures, see: Selvanayagam et al. (2011 ▶); Ali et al. (2010 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C₂₇H₂₄N₂O₃
M _r = 424.48
Monoclinic,
a = 10.4543 (3) Å
b = 14.6018 (4) Å
c = 14.7266 (4) Å
β = 104.043 (2)°
V = 2180.85 (10) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 293 K
0.26 × 0.23 × 0.18 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.978, T _max = 0.985
30221 measured reflections
7055 independent reflections
4544 reflections with I > 2σ(I)
R _int = 0.031

Refinement

R[F ² > 2σ(F ²)] = 0.050
wR(F ²) = 0.153
S = 1.02
7055 reflections
291 parameters
H-atom parameters constrained
Δρ_max = 0.31 e Å⁻³
Δρ_min = −0.23 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/S1600536811051440/bt5735sup1.cif

e-68-00o11-sup1.cif^{(24.4KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811051440/bt5735Isup2.hkl

e-68-00o11-Isup2.hkl^{(338.3KB, 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
N2—H2⋯O1ⁱ	0.86	2.02	2.874 (1)	174
C5—H5B⋯O3ⁱⁱ	0.96	2.59	3.407 (2)	143

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

Acknowledgments

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

supplementary crystallographic information

Comment

Highly functionalized pyrrolidines have gained much interest in the past few years as they constitute the main structural element of many natural and synthetic pharmacologically active compounds (Waldmann, 1995). Optically active pyrrolidines have been used as intermediates, chiral ligands or auxiliaries in controlled asymmetric synthesis (Suzuki et al., 1994; Huryn et al., 1991). In view of this importance, the crystal structure of the title compound has been carried out and the results are presented here.

The title compound consists of a pyrrolidine ring connected to a oxindole ring system at C1, a coumarine moiety at C2 and a benzene ring at C3. The X-ray analysis confirms the molecular structure and atom connectivity as illustrated in Fig.1.

The pyrrolidine (N1/C1–C4) ring adopts a twist conformation , with twist about the C4—N1 bond; the puckering parameters (Cremer & Pople, 1975), q₂ = 0.4216 (14) Å and φ₂ = 156.9 (2)°, and asymmetry parameters (Duax et al., 1976) ΔC₂[C4—N1] = 5.0 Å. The six membered pyranone ring (O2/C2/C13/C14/C19/C20) of the coumarine moiety adopts screw-boat conformation as indicated from the puckering parameters: Q = 0.5296 (15) Å, θ = 65.9 (2)° and φ = 215.9 (2)°. The oxindole unit (N2/C1/C6–C12) is essentially planar [maximum deviation = 0.048 (1) Å for the C1 atom] and is oriented at a dihedral angles of 87.1 (1)° and 28.6 (1)°, respectively, with the pyrrolidine and coumarine rings. The sum of angles at N1 of the pyrrolidine ring (337°) is in accordance with sp³ hybridization, and the sum of angles at N2 of the indole moiety (360°) is in accordance with sp² hybridization. The geometric parameters of the title molecule agrees well with those reported for similar structures (Selvanayagam et al., 2011; Ali et al., 2010).

Ihe molecular structure is stabilized by C3—H3···O3 and C13—H13A···O1 intramolecular hydrogen bonds, forming S(5) and S(6) ring motifs, respectively (Bernstein et al., 1995) (Table 1). The molecular structure is further stabilized by an intramolecular π—π interactions with Cg1—Cg2 seperation of 3.539 (1) Å. (Fig. 2; Cg1 and Cg2 are the centroids of the (N2/C1/C6/C7/C12) indole ring, (C14–C19) benzene ring, respectively). The crystal packing is stabilized by intermolecular N—H···O and C—H···O hydrogen bonds. The molecules at x, y, z and 2-x, 2-y, -z are linked by N2—H2···O1 hydrogen bonds into cyclic centrosymmetric R₂²(8) dimers. This dimers are further connected by C5—H5B···O3 hydrogen bonds forming supramolecular zig zag chains along the c axis (Fig. 3).

Experimental

A mixture of E-3-(4-methylbenzylidene)chroman-2-one (0.125 g, 0.5 mmol), isatin (0.08 g, 0.55 mmol) and N- methylglycine (0.025 g, 0.55 mmol) in toluene (5 ml) as solvent was allowed to reflux for 6 hours. After work up, the crude mass was purified by column chromatography to yield the pure product (0.195 g, 92% yield). The compound was recrystallized from ethyl acetate solvent. Single crystals suitable for X-ray diffraction were obtained by slow evaporation of a ethylacetate solution at room temperature.