6′-(1,3-Diphenyl-1H-pyrazol-4-yl)-7′-(1H-indol-3-ylcarbon­yl)-2-oxo-1-(prop-2-en-1-yl)-5′,6′,7′,7a’-tetra­hydro-1′H-spiro­[indoline-3,5′-pyrrolo­[1,2-c][1,3]thia­zole]-7′-carbo­nitrile

Piskala Subburaman Kannan; Devaraj Kathirvelan; Boreddy Siva Rami Reddy; Elumalai Govindan; Arunachalathevar SubbiahPandi

doi:10.1107/S1600536813011513

. 2013 May 11;69(Pt 6):o857–o858. doi: 10.1107/S1600536813011513

6′-(1,3-Diphenyl-1H-pyrazol-4-yl)-7′-(1H-indol-3-ylcarbonyl)-2-oxo-1-(prop-2-en-1-yl)-5′,6′,7′,7a’-tetrahydro-1′H-spiro[indoline-3,5′-pyrrolo[1,2-c][1,3]thiazole]-7′-carbonitrile

Piskala Subburaman Kannan ^a, Devaraj Kathirvelan ^b, Boreddy Siva Rami Reddy ^b, Elumalai Govindan ^c, Arunachalathevar SubbiahPandi ^c,^*

PMCID: PMC3684939 PMID: 23795041

Abstract

In the title compound, C₄₁H₃₂N₆O₂S, the pyrrolothiazole ring system is folded about the bridging N—C bond. The thiazolidine and pyrrolidine rings adopt envelope (with the fused C atom as the flap) and twisted conformations, respectively. The two phenyl rings attached to the pyrazole ring are twisted from the plane of the latter by 6.8 (1) and 52.8 (1)°. The allyl group is disordered over two conformations in a 0.805 (6):0.195 (6) ratio. In the crystal, pairs of N—H⋯O hydrogen bonds link the molecules into centrosymmetric dimers.

Related literature

For the biological activity of spiroheterocycles, see: Kilonda et al. (1995 ▶); Ferguson et al. (2005 ▶). For related structures, see: Jagadeesan et al. (2012a ▶,b ▶). For ring conformations, see: Cremer & Pople (1975 ▶).

Experimental

Crystal data

C₄₁H₃₂N₆O₂S
M _r = 672.80
Monoclinic,
a = 10.7396 (10) Å
b = 16.3471 (14) Å
c = 20.112 (2) Å
β = 105.485 (4)°
V = 3402.7 (6) Å³
Z = 4
Mo Kα radiation
μ = 0.14 mm⁻¹
T = 293 K
0.30 × 0.25 × 0.20 mm

Data collection

Bruker SMART APEXII area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2008 ▶) T _min = 0.958, T _max = 0.972
25634 measured reflections
5983 independent reflections
3281 reflections with I > 2σ(I)
R _int = 0.049

Refinement

R[F ² > 2σ(F ²)] = 0.049
wR(F ²) = 0.146
S = 1.06
5983 reflections
483 parameters
48 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.40 e Å⁻³
Δρ_min = −0.30 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 ▶); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ▶).

Supplementary Material

Click here for additional data file.^{(32.8KB, cif)}

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536813011513/cv5404sup1.cif

e-69-0o857-sup1.cif^{(32.8KB, cif)}

Click here for additional data file.^{(292.9KB, hkl)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813011513/cv5404Isup2.hkl

e-69-0o857-Isup2.hkl^{(292.9KB, hkl)}

Click here for additional data file.^{(12.8KB, cml)}

Supplementary material file. DOI: 10.1107/S1600536813011513/cv5404Isup3.cml

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
N5—H5A⋯O1ⁱ	0.92 (4)	1.92 (4)	2.822 (4)	166 (3)

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Symmetry code: (i) Inline graphic .

Acknowledgments

The authors thank the TBI X-ray facility, CAS in Crystallography and BioPhysics, University of Madras, Chennai, India, for the data collection.

supplementary crystallographic information

Comment

The design and synthesis of glycospiroheterocycles are important in view of their biological profile against viruses, bacteria, and cancer cells (Ferguson et al., 2005). Pyrrolidines and pyrroles are common structural motifs in drugs and drug candidates owing to their ability to act as selective glycosidase inhibitors, which are used in the treatment of diabetes, cancer, malaria and viral infections, including AIDS (Kilonda et al., 1995). Herewith we present the title compound (I), obtained in our group and containing glycospiroheterocycles.

In (I) (Fig. 1), the indole ring system(C1-C8/N6) is essentially planar (r.m.s.deviation = -0.064 Å ). The pyrollidine ring C8/C11-C13/N1) forms dihedral angle of 60.3 (1) with thiazole ring (C9-C11/N1/S1). The thiazole ring adopts an envelope conformation on C11 atom, with the puckering parameters of q₂ = 0.363 (3) Å, φ = 285.6 (5)° (Cremer & Pople, 1975). The pyrollidine ring adopts twisted conformation on C11-C12 atom, with the puckering parameters of q₂ = 0.367 (3) Å, φ = 301.1 (5)°. The allyl group is disordered over two conformations in a ratio 0.805 (6):0.195 (6). The crystal packing features are intermolecular N—H···O hydrogen bonds (Table 1), which link the molecules into centrosymmetric dimers.

Experimental

A mixture of allyl Isatin (1 mmol), thiaproline(1.1 mmol) and (2E)-3-(1,3- diphenyl-1H-pyrazol-4-yl)-2-[(E)-(1H-indol-3-yl) carbonyl] prop-2-enenitrile (1.3 mmol) were refluxed in ethanol (5 mL) for about 3 h. Completion of the reaction was evidenced by TLC analysis. After completion of the reaction, the reaction mixture was poured into ice-water, the resulting solid was filtered off and purified by column chromatography using ethyl acetate/Ether (6:4) as an eluent to afford pure spirooxindole.The block shaped single crystals of the title compound suitable for X-ray diffraction were obtained from solution of ethyl acetate/Ether (6:4) by slow evaportion at room temperature.