Methyl 6′-amino-5′-cyano-2′-methyl-2-oxospiro­[indoline-3,4′-pyran]-3′-carboxyl­ate

Song-Lei Zhu; Ting Liu

doi:10.1107/S1600536810053274

. 2010 Dec 24;67(Pt 1):o238. doi: 10.1107/S1600536810053274

Methyl 6′-amino-5′-cyano-2′-methyl-2-oxospiro[indoline-3,4′-pyran]-3′-carboxylate

Song-Lei Zhu ^a,^*, Ting Liu ^a

PMCID: PMC3050260 PMID: 21522738

Abstract

In the molecule of the title compound, C₁₆H₁₃N₃O₄, the atoms of the spiro pyran ring are nearly planar with a maximum deviation of 0.095 (2) Å. The indole and pyran rings are oriented at a dihedral angle of 87.3 (9)°. In the crystal, molecules are linked by intermolecular N—H⋯N and N—H⋯O hydrogen bonds.

Related literature

For the indole nucleus, see: Da-Silva et al. (2001 ▶). Compounds carrying the indole moiety exhibit antibacterial and fungicidal activity, see: Joshi & Chand (1982 ▶). Spirooxindole ring systems are found in a number of alkaloids like horsifiline, spirotryprostatin and elacomine, see: Abdel-Rahman et al. (2004 ▶). For our work on the preparation of heterocyclic compounds involving indole derivatives, see: Zhu et al. (2007 ▶).

Experimental

Crystal data

C₁₆H₁₃N₃O₄
M _r = 311.29
Monoclinic,
a = 15.0260 (15) Å
b = 10.0614 (11) Å
c = 10.4862 (12) Å
β = 105.956 (1)°
V = 1524.3 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 298 K
0.48 × 0.46 × 0.30 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.954, T _max = 0.971
7311 measured reflections
2686 independent reflections
1868 reflections with I > 2σ(I)
R _int = 0.032

Refinement

R[F ² > 2σ(F ²)] = 0.045
wR(F ²) = 0.127
S = 1.04
2686 reflections
210 parameters
H-atom parameters constrained
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.26 e Å⁻³

Data collection: SMART (Bruker, 2004 ▶); cell refinement: SAINT (Bruker, 2004 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810053274/bx2334sup1.cif

e-67-0o238-sup1.cif^{(19.1KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810053274/bx2334Isup2.hkl

e-67-0o238-Isup2.hkl^{(131.9KB, 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
N1—H1⋯N3ⁱ	0.86	2.09	2.928 (3)	165
N2—H2A⋯O1ⁱⁱ	0.86	2.17	2.925 (2)	147
N2—H2B⋯O1ⁱⁱⁱ	0.86	2.34	3.022 (2)	136

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

Acknowledgments

This work was partially supported by the Natural Science Foundation of Higher Education Institutions of Jiangsu Province (grant No. 09KJB150012) and the Special Presidential Foundation of Xuzhou Medical College (grant Nos. 09KJZ19 and 2010KJZ20) and the Open Foundation of the Key Laboratory of Cancer Biotherapy of Xuzhou Medical College (grant No. C0901).

supplementary crystallographic information

Comment

The indole nucleus is the well known heterocycle (Da-Silva et al., 2001). Compounds carrying the indole moiety exhibit antibacterial and fungicidal activities (Joshi & Chand, 1982). Spirooxindole ring systems are found in a number of alkaloids like horsifiline, spirotryprostatin and elacomine (Abdel-Rahman et al., 2004). As a part of our programme devoted to the preparation of heterocyclic compounds involving indole derivatives (Zhu et al., 2007), we have synthesized a series of spirooxindoles via reactions of isatins together with malononitrile and methyl 3-oxobutanoate in water. We report herein the crystal structure of the title compound, (I), (Fig. 1). The new formed spiro pyran ring A (O2/C2/C10/C11/C14/C15) adopts nearly planar conformation. The indole system and pyran ring are oriented at a dihedral angle of 87.3 (9)°. In the crystal structure, the molecules are linked by intermolecular N—H···N and N—H···O hydrogen bonds, Table 1, (Fig. 2).

Experimental

Compound (I) was prepared by the reaction of isatin (1 mmol), malononitrile (1 mmol) and methyl 3-oxobutanoate (1 mmol) in water (5 ml). The reaction was catalyzed by TEBAC (triethylbenzylammonium chloride, 1 mmol). After stirring at 333 K for 5 h, the reaction mixture was cooled and washed with small amount of ethanol. The crude product was filtered and single crystals of the title compound were obtained from ethanol solution by slow evaporation at room temperature (yield; 82%, m.p. 535-536 K). Spectroscopic analysis: IR (KBr, ν , cm^-1): 3458, 3362, 3217, 2212, 1729, 1628, 1464, 1376, 1284, 1210, 1057, 751, 676, 622. ¹H NMR (400 MHz, DMSO-d₆): 10.32 (s, 1H, NH), 7.21-7.25 (m, 3H, NH₂ + ArH), 6.97-7.03 (m, 2H, ArH), 6.78 (d, J = 10.4 Hz, 1H, ArH), 3.76 (s, 3H, CH₃), 2.25 (s, 3H, CH₃).