1′,6-Dimethyl-4′-phenyl­dispiro­[1-benzopyran-3(4H),3′-pyrrolidine-2′,3′′-indoline]-2,2′′-dione

D Lakshmanan; S Murugavel; D Kannan; M Bakthadoss

doi:10.1107/S1600536811050768

. 2011 Nov 30;67(Pt 12):o3516–o3517. doi: 10.1107/S1600536811050768

1′,6-Dimethyl-4′-phenyldispiro[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: PMC3239137 PMID: 22199985

Abstract

In the title compound, C₂₇H₂₄N₂O₃, the five-membered pyrroldine ring adopts an envelope conformation (with the N atom in the flap position) and the six-membered pyranone ring of the coumarine ring system adopts a slightly distorted boat conformation. The oxindole unit makes dihedral angles of 89.7 (1) and 25.6 (1)°, respectively, with the pyrrolidine ring and the coumarin ring system. The molecular structure is stabilized by two intramolecular C—H⋯O contacts and two intramolecular π–π interactions [centroid–centroid seperations of 3.514 (1) and 3.623 (1) Å]. The crystal packing features N—H⋯O hydrogen bonds, which link the molecules into cyclic centrosymmetric R ₂ ²(8) dimers, and C—H⋯π interactions.

Related literature

For background to the applications of pyrrolidine derivatives, see: Huryn et al. (1991 ▶) ; Suzuki et al. (1994 ▶); Waldmann (1995 ▶). For ring puckering analysis, see: Cremer & Pople (1975 ▶) . For closely related pyrrolidine structures, see: Selvanayagam et al. (2011 ▶); Ali et al. (2010 ▶).

Experimental

Crystal data

C₂₇H₂₄N₂O₃
M _r = 424.48
Monoclinic,
a = 11.1019 (5) Å
b = 11.1740 (4) Å
c = 17.8156 (7) Å
β = 100.986 (2)°
V = 2169.57 (15) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 293 K
0.25 × 0.22 × 0.17 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.979, T _max = 0.986
20613 measured reflections
4481 independent reflections
3019 reflections with I > 2σ(I)
R _int = 0.033

Refinement

R[F ² > 2σ(F ²)] = 0.043
wR(F ²) = 0.116
S = 1.02
4481 reflections
291 parameters
H-atom parameters constrained
Δρ_max = 0.17 e Å⁻³
Δρ_min = −0.18 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/S1600536811050768/bt5722sup1.cif

e-67-o3516-sup1.cif^{(24.5KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811050768/bt5722Isup2.hkl

e-67-o3516-Isup2.hkl^{(215.1KB, hkl)}

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

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

Cg2 is the centroid of the C7–C12 benzene ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C13—H13A⋯O1	0.97	2.44	3.114 (2)	126
C26—H26⋯O1	0.93	2.48	3.265 (2)	142
N2—H2⋯O1ⁱ	0.86	2.06	2.852 (2)	153
C18—H18⋯Cg2ⁱⁱ	0.93	2.88	3.758 (2)	157

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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 an envelope conformation with the N1 (displacement = 0.7 (2) Å) atom as the flap atom and with puckering parameters (Cremer & Pople, 1975),q₂ = 0.3935 (17) Å and φ₂ = 181.8 (2)°. 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 = 0.5042 (16) Å, θ = 69.5 (2)° and φ = 208.3 (2)°. The oxindole unit (N2/C1/C6–C12) is essentially planar [maximum deviation = 0.049 (2) Å for the C1 atom] and is oriented at a dihedral angles of 89.7 (1)° and 25.6 (1)°, respectively, with the pyrrolidine and coumarine rings. The sum of angles at N1 of the pyrrolidine ring (336°) 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 four intramolecular C—H···O contacts (Table 1). The molecular structure is further stabilized by intramolecular π—π interactions with Cg1—Cg3 and Cg2—Cg3 seperations of 3.513 (1) Å and 3.623 (1) Å, respectively (Fig. 2; Cg1, Cg2 and Cg3 are the centroids of the (N2/C1/C6/C7/C12) indole ring, (C7–C12) benzene ring and (C14–C19) benzene ring, respectively). The crystal packing is stabilized by intermolecular N—H···O hydrogen bonds. The molecules at x, y, z and 1-x, -y, -z are linked by N2—H2···O1 hydrogen bonds into cyclic centrosymmetric R₂²(8) dimers (Fig. 3). The crystal packing (Fig. 4) is further stabilized by C—H···π interactions between a H18 atom and a neighbouring benzene ring (C7–C12), with a C18—H8···Cg2ⁱⁱ seperation of 2.88 Å ( Fig. 4 and Table 1; Cg2 is the centroid of the C7–C12 benzene ring, Symmetry code as in Fig. 4).

Experimental

A mixture of E-3-benzylidene-6-methylchroman-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 (0.199 g, 94 % 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.