Crystal structure of 15-(naphthalen-1-yl)-7,7a,8,9,10,11-hexa­hydro-6a,12a-(methano­epoxy­methano)­indolizino[2,3-c]quinoline-6,13(5H)-dione

M P Savithri; M Suresh; R Raghunathan; R Raja; A SubbiahPandi

doi:10.1107/S2056989015002017

. 2015 Feb 7;71(Pt 3):o150–o151. doi: 10.1107/S2056989015002017

Crystal structure of 15-(naphthalen-1-yl)-7,7a,8,9,10,11-hexahydro-6a,12a-(methanoepoxymethano)indolizino[2,3-c]quinoline-6,13(5H)-dione

M P Savithri ^a, M Suresh ^b, R Raghunathan ^b, R Raja ^c, A SubbiahPandi ^c,^*

PMCID: PMC4350735 PMID: 25844221

Abstract

In the title compound, C₂₇H₂₄N₂O₃, the dihedral angle between the mean planes of the dihydrofuran and 3,4-dihydroquinoline ring systems is 70.65 (9)°. The dihydrofuran ring adopts an envelope conformation with the C atom adjacent to the methylene C atom of the pyrrolidine ring as the flap. The five-membered pyrrolidine ring adopts a twist conformation on the N—C(tetrasubstituted) bond. In the crystal, molecules are linked via pairs of N—H⋯O hydrogen bonds, forming inversion dimers with an R ₂ ²(8) ring motif. The dimers are linked via pairs of C—H⋯O hydrogen bonds, forming ribbons enclosing R ₂ ²(12) ring motifs lying in a plane parallel to (01-1).

Keywords: crystal structure, quinoline, pyrrolidine, hydrogen bonds

Related literature

For general background to quinoline and pyrrolidine derivatives, see: Padwa et al. (1999 ▸). For a related structure, see: Govindan et al. (2014 ▸). graphic file with name e-71-0o150-scheme1.jpg

Experimental

Crystal data

C₂₇H₂₄N₂O₃
M _r = 424.49
Triclinic,
a = 9.4184 (3) Å
b = 9.8804 (4) Å
c = 12.5401 (5) Å
α = 95.341 (2)°
β = 107.535 (2)°
γ = 99.940 (2)°
V = 1082.87 (7) Å³
Z = 2
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 293 K
0.35 × 0.30 × 0.30 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2004 ▸) T _min = 0.971, T _max = 0.975
28346 measured reflections
3817 independent reflections
3007 reflections with I > 2σ(I)
R _int = 0.023

Refinement

R[F ² > 2σ(F ²)] = 0.040
wR(F ²) = 0.157
S = 0.87
3817 reflections
293 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.17 e Å⁻³
Δρ_min = −0.21 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 for Windows (Farrugia, 2012 ▸); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ▸).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989015002017/su5066sup1.cif

e-71-0o150-sup1.cif^{(25.1KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015002017/su5066Isup2.hkl

e-71-0o150-Isup2.hkl^{(183.3KB, hkl)}

Click here for additional data file.^{(8.5KB, cml)}

Supporting information file. DOI: 10.1107/S2056989015002017/su5066Isup3.cml

Click here for additional data file.^{(1.3MB, tif)}

. DOI: 10.1107/S2056989015002017/su5066fig1.tif

The molecular structure of the title compound, showing the atom labelling. Displacement ellipsoids are drawn at the 30% probability level.

Click here for additional data file.^{(1.4MB, tif)}

b . DOI: 10.1107/S2056989015002017/su5066fig2.tif

A partial view along the b axis of the crystal packing of the title compound. The hydrogen bonds are shown as dashed lines (see Table 1 for details).

Click here for additional data file.^{(2.6MB, tif)}

a . DOI: 10.1107/S2056989015002017/su5066fig3.tif

The molecular packing viewed along the a axis. Dashed lines shows the intermolecular C—H⋯O and N—H⋯O hydrogen bonds (see Table 1 for details).

CCDC reference: 1046441

Additional supporting information: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (, ).

DHA	DH	HA	D A	DHA
N1H1AO3ⁱ	0.94(3)	1.92(3)	2.8413(19)	167(2)
C24H24O1ⁱⁱ	0.93	2.59	3.268(2)	131

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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

S1. Structural commentary

A large number of natural products contain the quinoline and indole heterocycles, and are found in numerous commercial products, including pharmaceuticals, fragrances and dyes (Padwa et al., 1999). In view of the above importance we have synthesized the title compound and report herein on its crystal structure.

The molecular structure of the title molecule is shown in Fig. 1. The furan ring system has an envelope conformation with atom C14 as the flap. The quinoline ring adopts a planar conformation with a maximum deviation of 0.326 (2) Å for the spiro C atom, C14. The five-membered pyrrolidine ring (N2/C13–C16) is twisted on N2—C13. The sum of the bond angles around atom N2 of the octahydroindolizine ring is 338.61° and for N1 of the quinoline ring it is 359.71°, confirming the sp³ and sp² hybridization, respectively.

In the crystal, molecules are linked by two pairs of N1—H1A···O3, C24—H24···O1 hydrogen bonds (Table 1), forming two inversion dimers and containing two R²₂(8), R²₂(12) ring motifs, respectively; see Fig. 2. In the crystal structure, intermolecular C24—H24···O1, N1—H1A···O3 hydrogen bonds link the molecules into ribbons lying parallel to the (011; Fig. 3 and Table 1.

S2. Synthesis and crystallization

A mixture of methyl 2-((hydroxyl(naphthalene-2-yl) methyl) acrylate (1 mmol), isatin (1.1 mmol) and pipecolic acid (1.1 mmol) was placed in a round bottom flask and melted at 180°C until completion of the reaction was evidenced by TLC analysis. After completion of the reaction, the crude product was washed with 5 ml of ethylacetate and hexane mixture (1:4 ratio) which successfully provided the pure product as colorless solid. The product was dissolved in ethyl acetate and heated for two minutes. The resulting solution was subjected to crystallization by slow evaporation of the solvent for 48 hours resulting in the formation of single crystals.

S3. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. All H atoms were fixed geometrically and allowed to ride on their parent C atoms, with C—H distances fixed in the range 0.93-0.98 Å with U_iso (H) = 1.5U_eq(C) for methyl H 1.2U_eq(C) for other H atoms.