Ethyl 1′′-benzyl-2′′-oxo-2′,3′,5′,6′,7′,7a’-hexa­hydro-1′H-di­spiro­[indeno­[1,2-b]quinoxaline-11,2′-pyrrolizine-3′,3′′-indoline]-1′-carboxyl­ate monohydrate

Piskala Subburaman Kannan; Srinu Lanka; Sathiah Thennarasu; Gopal Vimala; Arunachalathevar SubbiahPandi

doi:10.1107/S1600536813011537

. 2013 May 11;69(Pt 6):o854–o855. doi: 10.1107/S1600536813011537

Ethyl 1′′-benzyl-2′′-oxo-2′,3′,5′,6′,7′,7a’-hexahydro-1′H-dispiro[indeno[1,2-b]quinoxaline-11,2′-pyrrolizine-3′,3′′-indoline]-1′-carboxylate monohydrate

Piskala Subburaman Kannan ^a, Srinu Lanka ^b, Sathiah Thennarasu ^b, Gopal Vimala ^c, Arunachalathevar SubbiahPandi ^c,^*

PMCID: PMC3684937 PMID: 23795039

Abstract

In the title compound, C₃₈H₃₂N₄O₃·H₂O, the quinoxaline–indene and pyrrolizine systems are essentially planar, with maximum deviations from their mean planes of 0.162 and 0.563 Å, respectively. The pyrrolizine ring forms dihedral angles of 88.53 (5) and 89.95 (8)° with the quinoxaline–indene system and the indoline ring, respectively. The central pyrrolidine ring has an envelope conformation with the C atom bearing the quinoxaline-indene system as the flap. The pyrrolidine ring of the indole system adopts an envelope conformation with the C atom bonded to the pyrrolizine ring N atom as the flap. The five-membered ring attached to the central pyrolidine ring adopts a twisted conformation. In the crystal, O—H⋯N and O—H⋯O hydrogen bonds between water molecules and pyrrolizine N and carbonyl O atoms together with C—H⋯O interactions result in chains along [100].

Related literature

For general background to spiro compounds and their biological activity, see: Pradhan et al. (2006 ▶); Saeedi et al. (2010 ▶); Dandia et al. (2011 ▶); He et al. (2003 ▶). For uses of pyrrolidine and quinoxaline derivatives, see: Amal Raj et al. (2003 ▶); Zarranz et al. (2003 ▶). For a related structure, see: Srinivasan et al. (2012 ▶). For ring conformations, see: Cremer & Pople (1975 ▶). For details of the synthesis, see: Azizian et al. (2005 ▶).

Experimental

Crystal data

C₃₈H₃₂N₄O₃·H₂O
M _r = 610.69
Triclinic,
a = 11.0527 (3) Å
b = 11.5834 (3) Å
c = 12.2015 (3) Å
α = 97.370 (1)°
β = 92.037 (1)°
γ = 96.810 (1)°
V = 1536.25 (7) Å³
Z = 2
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 = 0.979, T _max = 0.984
21165 measured reflections
5410 independent reflections
4751 reflections with I > 2σ(I)
R _int = 0.027

Refinement

R[F ² > 2σ(F ²)] = 0.040
wR(F ²) = 0.114
S = 1.02
5410 reflections
422 parameters
3 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.27 e Å⁻³
Δρ_min = −0.31 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.^{(30.8KB, cif)}

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536813011537/bx2437sup1.cif

e-69-0o854-sup1.cif^{(30.8KB, cif)}

Click here for additional data file.^{(259.5KB, hkl)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813011537/bx2437Isup2.hkl

e-69-0o854-Isup2.hkl^{(259.5KB, 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
O4—H4A⋯N2	0.99 (2)	2.03 (2)	2.996 (2)	164 (2)
O4—H4B⋯O1ⁱ	0.99 (2)	2.31 (2)	3.222 (2)	154 (2)
C2—H2⋯O1ⁱⁱ	0.93	2.50	3.393 (2)	162
C24—H24A⋯O4ⁱⁱⁱ	0.97	2.56	3.495 (3)	163

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

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

Spiro compounds have received considerable interest due to their highly biological properties (Pradhan et al., 2006); Thus more and more novel spiroheterocycle compounds have been prepared and characterized (Saeedi et al., 2010); Dandia et al., 2011). In addition , quinoxaline derivatives also showed various biological activites (He et al., 2003).

Pyrrolidine derivatives are found to have anticonvulsant, antimicrobial and antifungal activities against various pathogens (Amal Raj et al., 2003). Quinoxaline derivatives shown antibacterial, antiviral and anticancer properties (Zarranz et al., 2003). As spiro pyrrolidine compounds are of great medicinal properties, we have undertaken the three dimensional structure of the title compound. In view of these importance and continuation of our work on the crystal structure analyis of pyrrolidine and quinoxaline 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 of the compound as illustrated in Fig. 1. The quinoxaline-indene systems (C1-C15/N1-N2) and pyrrolizine system (C15-C16/C34-C38/N4), are essentially planar, with maximum deviations from mean plane of -0.162 Å for C3 atom and -0.563 Å for C36 atom, respectively.

The pyrrolizine ring (C15-C16/C34-C38/N4) forms a dihedral angles of 88.53 (5) and 89.95 (6)° with quinoxaline-indene systems and indole ring (C16-C23/N3) respectively. This clearly shows that the quinoxaline-indene ring system and indole rings are almost perpendicular to the pyrrolizine ring. The central pyrrolidine ring (C15-C16/C34-C35/N4) is enveloped on C15 with the puckering parameters of q₂ = 0.4478 (2) Å, φ = 246.90 (2)° (Cremer & Pople, 1975). The pyrrolidine (C16-C18/C23/N3) of indole ring adopts envelope conformation on C16 with the puckering parameters of q₂ = 0.0729 (2) Å, φ = 243.08 (1)°. The five membered ring (C35-C38/N4) attached with the central pyrolidine ring adopts twisted conformation on C36-C37 with the puckering parameters of q₂ = 0.3767 (2) Å, φ = 92.96 (3)°.

In the crystal intra and intermolcular O-H···O hydrogen bonds between water molecules and pyrrolizine fragment N and carbonyl group O atoms of organic compound together with C-H···O interactions result in one-dimensional supramolecular structure.

Experimental

Benzyl Isatin( 0.25 mmol), L-proline ( 0.3 mmol), Ethyl Indeno[1,2-b] quinoxalin-11-ylideneacetate( 0.25 mmol) (Azizian et al., 2005) in ethanol refluxed for 60 min. The progress of the reaction was followed by TLC. After completion, the solvent was removed under reduced pressure and the resulting crude product was subjected to column chromatography. The product was recrystallised from methanol. Single crystals suitable for X-ray diffraction were obtained by slow evaporation of the solution of the title compound in methanol at room temperature.