1′,1′′-Dimethyl-4′-(4-methyl­phen­yl)di­spiro­[11H-indeno­[1,2-b]quinoxaline-11,2′-pyrrolidine-3′,3′′-piperidin]-4′′-one

R A Nagalakshmi; J Suresh; K Malathi; R Ranjith Kumar; P L N Lakshman

doi:10.1107/S1600536813022964

. 2013 Aug 23;69(Pt 9):o1466. doi: 10.1107/S1600536813022964

1′,1′′-Dimethyl-4′-(4-methylphenyl)dispiro[11H-indeno[1,2-b]quinoxaline-11,2′-pyrrolidine-3′,3′′-piperidin]-4′′-one

R A Nagalakshmi ^a, J Suresh ^a, K Malathi ^b, R Ranjith Kumar ^b, P L N Lakshman ^c,^*

PMCID: PMC3884467 PMID: 24427088

Abstract

In the title compound, C₃₁H₃₀N₄O, the central pyrrolidine ring adopts an envelope conformation with the methylene C atom being the flap. The quinoxaline and indane rings are each planar, having r.m.s. deviations of 0.030 and 0.050 Å, respectively. The pyrrolidine ring mean plane forms dihedral angles of 88.25 (1) and 83.76 (1)° with the quinoxaline and indane rings, respectively. Intramolecular C—H⋯O and C—H⋯N interactions are observed. In the crystal, C—H⋯π interactions lead to helical supramolecular chains along the b-axis direction.

Related literature

For the importance of pyrrolidine compounds, see: Witherup et al. (1995 ▶). For the importance of heterocycles with piperidine sub-structures, see: El-Subbagh et al. (2000 ▶); Dimmock et al. (2001 ▶); Lee et al. (2001 ▶). For additional conformation analysis, see: Cremer & Pople (1975 ▶).

Experimental

Crystal data

C₃₁H₃₀N₄O
M _r = 474.59
Monoclinic,
a = 22.3183 (7) Å
b = 14.4411 (5) Å
c = 17.2474 (6) Å
β = 116.547 (2)°
V = 4972.8 (3) Å³
Z = 8
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 293 K
0.21 × 0.19 × 0.18 mm

Data collection

Bruker Kappa APEXII diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.967, T _max = 0.974
22517 measured reflections
4550 independent reflections
3034 reflections with I > 2σ(I)
R _int = 0.031

Refinement

R[F ² > 2σ(F ²)] = 0.042
wR(F ²) = 0.124
S = 1.04
4550 reflections
327 parameters
H-atom parameters constrained
Δρ_max = 0.18 e Å⁻³
Δρ_min = −0.12 e Å⁻³

Data collection: APEX2 (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: PLATON (Spek, 2009 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536813022964/tk5247sup1.cif

e-69-o1466-sup1.cif^{(27KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813022964/tk5247Isup2.hkl

e-69-o1466-Isup2.hkl^{(218.5KB, 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
C3—H3⋯O1	0.98	2.36	2.804 (2)	107
C41—H41B⋯N3	0.97	2.39	2.980 (2)	119
C11—H11⋯Cg1ⁱ	0.93	2.94	3.692 (2)	139

Open in a new tab

Symmetry code: (i) Inline graphic .

Acknowledgments

JS and RAN thank the management of the Madura College for their encouragement and support. RRK thanks the DST, New Delhi, for funds under their fast-track scheme (No. SR/FT/CS-073/2009)

supplementary crystallographic information

1. Comment

Pyrrolidine-containing compounds are of significant importance because of their biological activities and widespread employment in catalysis (Witherup et al., 1995). Heterocycles with piperidine sub-structures display important biological activities, such as cytotoxic (El-Subbagh et al., 2000) and anti-cancer (Dimmock et al., 2001) besides being useful as synthons in the construction of alkaloid natural products (Lee et al., 2001). The high medicinal value of these compounds, in conjunction with our research interests, prompted us to synthesize and report the X-ray studies of the title compound.

In the title compound (Fig. 1), the central pyrrolidine ring is an envelope on C2 with asymmetry parameters ΔC_s(C2) = 7.1 (2)° and puckering parameters q₂ = 0.4303 (18) Å and φ₂ = 211.5 (2)° (Cremer & Pople, 1975). The quinoxaline and the indane group forms dihedral angles of 88.25 (1) and 83.76 (1)°, respectively, with the central pyrrolidine ring. The quinoxaline ring system (C12—C17/N3,N4) is planar, with r.m.s. deviation = 0.030 Å. The indane group is also planar with r.m.s deviation = 0.050 Å. The dihedral angle between the mean planes of the fused quinoxaline and the indane groups is 8.43 (1)°, indicate that the fused rings is slightly folded about the C12—C13 bond. The six-membered ring, N2/C41—C45, exhibits a twisted chair conformation, as indicated by the asymmetry parameters ΔC_s(N2) = 7.58 (16)°, ΔC_s(C45) = 7.58 (16)° and with the puckering parameters Q = 0.558 (2) Å, Θ = 164.1 (2)° and Φ = 207.1 (8)°. The torsion angle C4—C42—N2—C42 is -167.62 (16)° and corresponds to an antiperiplanar conformation. The sum of bond angles around N1(339.9°) and N2 (331.4°) indicate the atoms N1 and N2 are each in a pyramidal geometry. Weak intramolecular C—H···O, N interactions are observed (Table 1). In the crystal structure, C—H···π interactions, involving the benzene ring C14···C19, lead to the helical supramolecular chains along the b axis, as shown in Fig. 2.

2. Experimental

A mixture of 1-methyl-3-[E-(4-methylphenyl)methylidene]tetrahydro-2(1H)- pyridinone (1 mmol), ninhydrin (1 mmol), o-phenylenediamine (1 mmol) and sarcosine (1 mmol) in methanol was refluxed for 3–4 h. After completion of the reaction as indicated by TLC the reaction mixture was poured into cold water. The solid precipitate obtained was filtered and dried. The product was purified by column chromatography using petroleum ether:ethylacetate mixture (90:10 v/v). Suitable crystals were obtained by recrystallizing the product from methanol. Yield: 37%, M. pt: 498–500 K.