1-Methyl-1′-(4-methyl­phen­yl)-2′,3′,5′,6′,7′,7a’-hexa­hydro-1′H-dispiro­[piperidine-3,2′-pyrrolizine-3′,3′′-indoline]-4,2′′-dione

S Ramaswamy; R Sribala; N Srinivasan; R V Krishnakumar; R Ranjith Kumar

doi:10.1107/S1600536812036240

. 2012 Aug 25;68(Pt 9):o2772–o2773. doi: 10.1107/S1600536812036240

1-Methyl-1′-(4-methylphenyl)-2′,3′,5′,6′,7′,7a’-hexahydro-1′H-dispiro[piperidine-3,2′-pyrrolizine-3′,3′′-indoline]-4,2′′-dione

S Ramaswamy ^a, R Sribala ^b, N Srinivasan ^b,^*, R V Krishnakumar ^b, R Ranjith Kumar ^c

PMCID: PMC3435806 PMID: 22969652

Abstract

The title compound, C₂₆H₂₉N₃O₂, crystallizes with two molecules in the asymmetric unit, having C—H⋯O interactions between them and resulting in a dimer characterized by an R ₂ ²(11) motif. These dimers are linked into an ABABAB chain via N—H⋯O, N—H⋯N and C—H⋯O built edge-fused R ₁ ²(5) and R ₂ ²(7) motifs. This chain is linked to its inversion-related partner via N—H⋯O bonds with an R ² ₂(8) motif and leads to a double chain extending along the b axis characterized by an R ₆ ⁶(36) motif across the inversion centres. The methyl group of the phenyl ring and the oxindole of molecule A and B are involved in C—H⋯π interactions. One C atom of the pyrrolizine ring of molecule A and its attached H atoms show positional disorder, the major and minor components being in the ratio 0.706 (7):0.294 (7).

Related literature

For ring puckering parameters, see: Cremer & Pople (1975 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C₂₆H₂₉N₃O₂
M _r = 415.52
Triclinic,
a = 8.7516 (4) Å
b = 12.4649 (5) Å
c = 21.4605 (8) Å
α = 97.654 (2)°
β = 101.024 (2)°
γ = 102.345 (2)°
V = 2207.45 (16) Å³
Z = 4
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 293 K
0.28 × 0.19 × 0.19 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T _min = 0.93, T _max = 0.96
44464 measured reflections
7765 independent reflections
5493 reflections with I > 2σ(I)
R _int = 0.037

Refinement

R[F ² > 2σ(F ²)] = 0.040
wR(F ²) = 0.110
S = 1.02
7765 reflections
574 parameters
H-atom parameters constrained
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.17 e Å⁻³

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: PLUTON (Spek, 2009 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812036240/fj2583sup1.cif

e-68-o2772-sup1.cif^{(56.2KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812036240/fj2583Isup2.hkl

e-68-o2772-Isup2.hkl^{(372.2KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

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

Cg1 and Cg2 are the centroids of the C20A–C25A and C20B–C25B rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2A—H2A⋯O1A ⁱ	0.86	1.99	2.8331 (17)	167
N2B—H2B⋯O1A ⁱⁱ	0.86	2.48	3.0829 (18)	128
N2B—H2B⋯N1A ⁱⁱ	0.86	2.24	3.0461 (18)	156
C4A—H4A⋯O1B ⁱⁱⁱ	0.98	2.52	3.4598 (19)	160
C16B—H16C⋯O2A	0.97	2.47	3.431 (2)	171
C5A—H52A⋯O2B	0.97	2.58	3.404 (2)	143
C6A—H63A⋯Cg1^iv	0.97	2.97	3.819 (9)	147
C6B—H62B⋯Cg2^iv	0.97	2.93	3.827 (3)	155

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

Acknowledgments

The authors thank the Sophisticated Analytical Instrumentation Facility (SAIF), Indian Institute of Technology, Chennai, for the X-ray intensity data collection.

supplementary crystallographic information

Comment

The title compound contains two molecules in the asymmetric unit forming an asymmetric dimer through C—H···O hydrogen bonds between them. The molecular structure with displacement ellipsoids drawn at 50% probability level is shown in Fig.1. The C8—O1 distance in the indolone in molecules A and B are 1.2244 (18)and 1.215 (2) A°, respectively. The difference in the C8—O1 bond distances in molecules A and B is substantiated by the deviation of O1 from the plane by about 0.4122 (18) in molecule A and 0.2907 (21) in molecule B. This deviation of O1 from planarity seems to have considerably influenced differences in the values of the torsion angles N1—C1–C8—O1 and C2—C1—C8—O1 of molecules A and B. In molecule A, these torsion angles are 37.5 (2) and -75.6 (2)° while in B these values are -53.8 (2) and 61.0 (2)°, respectively. These differences in conformation may also be attributed to a significant intermolecular feature that O1A participates in a three-centered hydrogen bond involving N—H···O and N—H···N types and O1B in a C—H···O type hydrogen bond.

The carbon atom C6 in the hexahydropyrrolizine ring of molecule A shows positional disorder with major and minor component of 0.71 and 0.29, respectively for its site occupancy factor. This disorder leads to a flipping of the conformation of the N1—C4—C5—C6—C7 ring with the puckering parameters (Cremer & Pople, 1975) observed as twisted on C5—C6 with q=0.393 Å, φ=271.4 (3)° for the major component and twisted on C6—C7 with q=0.347 (5) Å, φ=125.0 (7) ° for the minor component. The corresponding ring in molecule B shows similar twist conformation but with the twist on N1—C4 with q=0.394 (2) Å, φ=15.9 (4) °. The puckering of the five-membered ring N1—C1—C2—C3—C4 of the pyrrolizine is envelope (³E) on atom C2 with q = 0.3615 (17) Å, φ = 66.3 (3)° in molecule A and envelope (E₅) on atom C4 with q = 0.4364 (19) Å, φ = 320.7 (2) ° in molecule B. The puckering of the piperidinone rings in both the molecules is close to the usual chair with Q = 0.551 (2) Å, θ = 24.0 (2)°, φ = 353.7 (8)° for molecule A and Q = 0.559 (2) Å, θ = 16.4 (2)°, φ = 339.4 (8)° for molecule B. The hydrogen-bonded interaction (Table 1) between molecules generate one-dimensional double chains extending along the b axis (Fig.2).

The molecular interaction pattern is characterized by four different graph-set motifs (Bernstein et al., 1995) viz.R²₂(8), R²₂(7), R²₁(5) and a R²₂(11) type. The R²₂(11) motif occurs between the two molecules in the asymmetric unit through C—H···O hydrogen bonds. The R²₂(8) is built across inversion centres through N—H···O hydrogen bonds. R²₂(7) is edge fused with a R²₁(6) motif, in which the N—H···N bond is the shared edge, while C—H···O and N—H···O, respectively are their respective characteristic units. An interesting feature is that all these fundamental simple graph-set motifs lead to a complex R⁶₆(36) motif across the inversion centres. Also two significant C—H···πviz. C6A—H63A···Cg1(C20A→C25A) and C6B—H62B···Cg2 (C20B→C25B) interactions are observed. Thus, the presence of a variety of interaction patterns in the crystal structure of a geometrically unfathomable molecule may well be regarded significant in the context of crystal structure prediction.