rac-Methyl (1R,3′S)-1′,1′′-dimethyl-2,2′′-dioxo-2H-dispiro­[acenaphthyl­ene-1,2′-pyrrolidine-3′,3′′-indoline]-4′-carboxyl­ate

G Ganesh; Panneer Selvam Yuvaraj; Chinthalapuri Divakara; Boreddy S R Reddy; A SubbiahPandi

doi:10.1107/S1600536813000470

. 2013 Jan 12;69(Pt 2):o235. doi: 10.1107/S1600536813000470

rac-Methyl (1R,3′S)-1′,1′′-dimethyl-2,2′′-dioxo-2H-dispiro[acenaphthylene-1,2′-pyrrolidine-3′,3′′-indoline]-4′-carboxylate

G Ganesh ^a, Panneer Selvam Yuvaraj ^b, Chinthalapuri Divakara ^b, Boreddy S R Reddy ^b, A SubbiahPandi ^c,^*

PMCID: PMC3569768 PMID: 23424514

Abstract

In the title compound, C₂₆H₂₂N₂O₄, the pyrrolidine ring adopts a twisted conformation and the other five-membered rings adopt envelope conformations with the spiro C atoms as the flap atoms. The naphthalene ring system of the dihydroacenaphthylene group forms dihedral angles of 89.2 (9) and 75.5 (6)° with the pyrrolidine and indole rings, respectively. The pyrrolidine ring makes a dihedral angle of 80.1 (9)° with the indole ring. In the crystal, molecules are linked by weak C—H⋯O hydrogen bonds, forming chains along the b-axis direction.

Related literature

For the biological activity of naphthalene derivatives, see: Wiltz et al. (1998 ▶); Wright et al. (2000 ▶); Varma et al. (1994 ▶). For a related structure, see: Wei et al. (2012 ▶). For ring conformations, see: Cremer & Pople (1975 ▶).

Experimental

Crystal data

C₂₆H₂₂N₂O₄
M _r = 426.46
Monoclinic,
a = 15.4839 (4) Å
b = 9.5832 (2) Å
c = 15.6375 (4) Å
β = 115.184 (1)°
V = 2099.81 (9) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 293 K
0.25 × 0.22 × 0.19 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2008 ▶) T _min = 0.977, T _max = 0.983
19264 measured reflections
4057 independent reflections
3017 reflections with I > 2σ(I)
R _int = 0.031

Refinement

R[F ² > 2σ(F ²)] = 0.038
wR(F ²) = 0.103
S = 1.03
4057 reflections
292 parameters
H-atom parameters constrained
Δρ_max = 0.17 e Å⁻³
Δρ_min = −0.17 e Å⁻³

Data collection: APEX2 (Bruker, 2008 ▶); cell refinement: SAINT (Bruker, 2008 ▶); 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 (Farrugia, 2012 ▶); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ▶).

Supplementary Material

Click here for additional data file.^{(31KB, cif)}

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536813000470/lx2278sup1.cif

e-69-0o235-sup1.cif^{(31KB, cif)}

Click here for additional data file.^{(198.9KB, hkl)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813000470/lx2278Isup2.hkl

e-69-0o235-Isup2.hkl^{(198.9KB, 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
C10—H10⋯O2ⁱ	0.93	2.60	3.268 (2)	130

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Symmetry code: (i) Inline graphic .

Acknowledgments

ASP thanks the University Grants Commission, India, for a Minor Research Project.

supplementary crystallographic information

Comment

Naphthalene derivatives have manifested applications in many fields, for example, as a colorant, explosive, disinfectant, insecticide and plant hormone auxin. Naphthalene is believed to play a role in the chemical defence against biological enemies (Wiltz et al., 1998; Wright et al., 2000). It may be produced by metabolic processes in termites or by associated microorganisms which inhabit, e.g., the termite guts (Varma et al., 1994). In view of these importance and continuation of our work on the crystal structure analyis of napthalene derivatives, the crystal structure of the title compound has been carried out and the results are presented here.

X–Ray analysis confirms the molecular structure and atom connectivity as illustrated in Fig. 1. The geometry of acenaphthylene and pyrrolidine ring systems are comparable with the related structure [Wei et al. (2012)]. The sum of the angles at N1 [338.2 (1)°] and N2 [359.4 (1)°] of the pyrrolidine rings are in accordance with sp³ and sp² hybridizations. The naphthalene ring system of the dihydroacenaphthylene group [C7–C16] forms dihedral angles of 89.2 (8) and 75.5 (5)° with the central pyrrolidine ring [N1/C2–C5] and the indole ring [N2/C4/C17–C23], respectively. It clearly shows that the naphthalene ring system of the dihydroacenaphthylene group attached to the central pyrrolidine ring are almost perpendicular to each other. Also the dihedral angle between the central pyrrolidine and the indole ring forms a a dihedral angle of 80.1 (8)°.

The central pyrrolidine ring adopts twisted conformations on N1 and C2 atoms with the pukering parameter of q₂ = 0.3942 (2) Å, φ = 13.72 (3)° (Cremer & Pople, 1975). The pyrrolidine ring [N2/C4/C17–C19] in the indole group adopts envelope conformations, q₂ = 0.0889 (2) Å and φ = 219.39 (1)°, and with atom C17 deviating -0.0565 (2) Å from the least–squares plane passing through the remaining four atoms (N2/C19/C18/C4) of that ring. In the crystal the molecules are linked by weak intermolecular C—H···O hydrogen bonds (Table 1), forming one-dimensional chains along the b–axis.

Experimental

To a mixture of 1eq of (E)–methyl 2–(1–methyl–2–oxoindolin –3–ylidene) acetate, 1eq of isatin and 1.5eq of acenaphthylene–1,2 –dione were dissolved in acetonitrile. This reaction mixture refluxed at 80°C for 8 hours. The reaction mixture was monitored for completion by thin layar chromatography. Upon completion, the reaction mixture was extracted with ethyl acetate and water. The product was dried and purified by coloumn chromatography using ethyl acetate and hexane (1:9) as an elutent to affored pure Dispiro oxindole. Yield (78%). Single crystals suitable for X–ray diffraction were obtained by slow evaporation of a solution of the title compound in ethyl acetate at room temperature.