Crystal structure of 4′-(2-meth­oxy­quinolin-3-yl)-1′-methyl­dispiro­[indan-2,2′-pyrrolidine-3′,3′′-indoline]-1,3,2′′-trione

Sadasivam Mathusalini; Vijayan Viswanathan; Palathurai Subramaniam Mohan; Chia-Her Lin; Devadasan Velmurugan

doi:10.1107/S2056989015023026

. 2015 Dec 12;71(Pt 12):o1038–o1039. doi: 10.1107/S2056989015023026

Crystal structure of 4′-(2-methoxyquinolin-3-yl)-1′-methyldispiro[indan-2,2′-pyrrolidine-3′,3′′-indoline]-1,3,2′′-trione

Sadasivam Mathusalini ^a, Vijayan Viswanathan ^b, Palathurai Subramaniam Mohan ^a,^*, Chia-Her Lin ^c, Devadasan Velmurugan ^b

PMCID: PMC4719967 PMID: 26870486

Abstract

In the title compound, C₃₀H₂₃N₃O₄, the central 1-methylpyrrolidine ring adopts a twist conformation on the N—CH₂ bond. The pyrrolidin-2-one ring of the indolin-2-one ring system also has a twist conformation on the C—C bond involving the spiro C atom and the carbonyl C atom. The five-membered ring of the indene-1,3-dione moiety has an envelope conformation with the spiro C atom as the flap. The quinoline ring system adopts an almost planar conformation (r.m.s. deviation = 0.04 Å). The mean planes of the indolin-2-one ring system, the indene-1,3-dione ring system and the the quinoline ring system are inclined to the mean plane of the central 1-methylpyrrolidine ring by 77.97 (7), 86.98 (7) and 46.58 (6)°, respectively. In the crystal, molecules are linked via N—H⋯N hydrogen bonds, forming chains along the b axis. The chains are linked via a number of C—H⋯O hydrogen bonds, and C—H⋯π and π–π interactions [inter-centroid distance = 3.7404 (9) Å], forming a three-dimensional network.

Keywords: crystal structure, spiro-indane, spiro-indolino, quinoline, pyrrolidine, hydrogen bonding

Related literature

For the biological activity of pyrrolidine and indole derivatives, see: Babu et al. (2012 ▸); Savithri et al. (2014 ▸); Govind et al. (2003 ▸); Gayathri et al. (2005 ▸); Li et al. (2004 ▸); Bellina & Rossi (2006 ▸). For the crystal structure of a similar dispiroindoline compound, see: Nirmala et al. (2009 ▸). graphic file with name e-71-o1038-scheme1.jpg

Experimental

Crystal data

C₃₀H₂₃N₃O₄
M _r = 489.51
Monoclinic,
a = 10.9058 (3) Å
b = 9.5178 (5) Å
c = 23.8651 (6) Å
β = 95.378 (2)°
V = 2466.27 (16) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 293 K
0.27 × 0.18 × 0.11 mm

Data collection

Bruker SMART APEXII area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2008 ▸) T _min = 0.976, T _max = 0.990
23642 measured reflections
6134 independent reflections
4376 reflections with I > 2σ(I)
R _int = 0.044

Refinement

R[F ² > 2σ(F ²)] = 0.044
wR(F ²) = 0.115
S = 1.03
6134 reflections
337 parameters
H-atom parameters constrained
Δρ_max = 0.31 e Å⁻³
Δρ_min = −0.22 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 for Windows (Farrugia, 2012 ▸) and Mercury (Macrae et al., 2008 ▸); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ▸).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989015023026/su5242sup1.cif

e-71-o1038-sup1.cif^{(27.1KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015023026/su5242Isup2.hkl

e-71-o1038-Isup2.hkl^{(294.2KB, hkl)}

Click here for additional data file.^{(5.4KB, cml)}

Supporting information file. DOI: 10.1107/S2056989015023026/su5242Isup3.cml

Click here for additional data file.^{(1.2MB, tif)}

. DOI: 10.1107/S2056989015023026/su5242fig1.tif

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

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

c b- . DOI: 10.1107/S2056989015023026/su5242fig2.tif

A partial view, along the c axis, of the crystal packing of the title compound, illustrating the formation of the hydrogen-bonded zigzag chains (dashed lines; see Table 1) running along the the b-axis direction. C-bound H atoms have been omitted for clarity.

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

b . DOI: 10.1107/S2056989015023026/su5242fig3.tif

A view along the b axis of the crystal packing of the title compound. Hydrogen bonds are shown as dashed lines and C—H⋯π interactions as blue arrows (see Table 1). H atoms not involved in these interactions have been omitted for clarity.

CCDC reference: 1439764

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

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

Cg1 is the centroid of the C3–C8 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3⋯N2ⁱ	0.86	2.19	2.971 (2)	151
C4—H4⋯O3ⁱⁱ	0.93	2.56	3.350 (2)	143
C6—H6⋯O4ⁱⁱⁱ	0.93	2.42	3.307 (2)	159
C12—H12A⋯O2^iv	0.97	2.53	3.325 (2)	139
C28—H28⋯O4ⁱ	0.93	2.56	3.354 (1)	144
C18—H18⋯Cg1^v	0.93	2.89	3.778 (6)	160

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) ; (v) .

Acknowledgments

The authors thank the X-ray facility, Department of Chemistry, Chung Yuan Christian University, Chung-Li 32023, Taiwan, for the data collection. SM is grateful to the UGC–BSR, Bahadurshah Zafar Marg, New Delhi 110 002, India, for financial support.

supplementary crystallographic information

S1. Comment

The pyrrolidine ring system is found in a vast variety of compounds displaying an impressive range of biological activities (Babu et al., 2012). Optically active pyrrolidines have been used as intermediates, chiral ligands or auxiliaries in controlled asymmetric synthesis (Savithri et al., 2014). Pyrrolidine compounds are reported to exhibit antimicrobial, antifungal (Govind et al., 2003), anti-influenza virus (Gayathri et al., 2005), anti-inflammatory, antitumor (Li et al., 2004), inhibit retroviral reverse transcriptases [i.e., human immunodeficiency virus type 1 (HIV-1)], cellular DNA polymerases, protein kinases (Bellina and Rossi, 2006), antibiotics (Nirmala et al., 2009), anticonvulsant, sphingosine-1-phosphate (S1P) receptor agonists, malic enzyme inhibitors, ketoamide-based cathepsin K inhibitors, human melanocortin-4 receptor agonists (Babu et al., 2012). Indole compounds can be used as bioactive drugs. Indole derivatives exhibit antiallergic, central nervous system depressant and muscle relaxant properties. In view of this biological importance, the title compound was synthesized and we report herein on its the crystal structure.

The molecular structure of the title compound is shown in Fig. 1. The central 1-methylpyrrolidine ring (N2/C11/C12/C14/C23) adopts a twist conformation on the N2—C12 bond. The pyrrolidine-2-one ring (N3/C23/C24/C29/C30) of the indoline-2-one ring system also has a twist conformation on the C23—C30 bond involving the spiro C atom and the carbonyl C atom. The five-membered ring (C14—C16/C21/C22) of the indene-1,3-dione moiety has an envelope conformation with atom C14 as the flap. The quinoline ring system adopts a planar conformation [r.m.s. deviation = 0.04 Å]. The mean planes of the indolin-2-one ring system, the indene-1,3-dione ring system and the the quinoline ring system are inclined to the mean plane of the central 1-methylpyrrolidine ring by 77.97 (7), 86.98 (7) and 46.58 (6) °, respectively.

In the crystal, molecules are linked via N—H···N hydrogen bonds forming zigzag chains along the b axis direction (Table 1 and Fig. 2). The chains are linked via number of C—H···O hydrogen bonds, and C—H···π and π-π interactions, involving inversion related quinoline units [Cg4···Cg5ⁱ = 3.7404 (9) Å; where Cg4 and Cg5 are the centroids of rings N1/C1—C3/C8/C9 and C3—C8; symmetry code: (i) -x, -y+1, -z+1], forming a three-dimensional structure (Table 1 and Fig. 3).

S2. Synthesis and crystallization

A mixture of indoline-2,3-dione (1 mmol) and 2-(methylamino)acetic acid (1.5 mmol) were dissolved in methanol (100 ml) and refluxed for 5 min, followed by the addition of (Z)-3-((2-methoxyquinolin-3-yl) methylene) indolin-2-one (0.5 mmol), then the mixture was refluxed for 8 h. After completion of the reaction (monitored by silicagel precoated TLC), the title compound was separated from the cooled reaction mixture, filtered and dried under reduced pressure. Slow evaporation of a solution on the title compound in chloroform/methanol (4:1) yielded light-yellow block-like crystals.

S3. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. The hydrogen atoms were placed in calculated positions and refined as riding atoms: C—H = 0.93-0.98 Å and N—H = 0.86 Å with U_iso(H) = 1.5U_eq(C-methyl) and 1.2U_eq(N,C) for other H atoms.