Methyl 9-(4-meth­oxy­phen­yl)-19-methyl-3,12-di­aza­penta­cyclo­[10.7.0.02,10.03,8.013,18]nona­deca-1(19),13(18),14,16-tetra­ene-10-carboxyl­ate

S Selvanayagam; B Sridhar; S Kathiravan; R Raghunathan

doi:10.1107/S1600536813010489

. 2013 Apr 20;69(Pt 5):o776. doi: 10.1107/S1600536813010489

Methyl 9-(4-methoxyphenyl)-19-methyl-3,12-diazapentacyclo[10.7.0.0^2,10.0^3,8.0^13,18]nonadeca-1(19),13(18),14,16-tetraene-10-carboxylate

S Selvanayagam ^a,^*, B Sridhar ^b, S Kathiravan ^c, R Raghunathan ^c

PMCID: PMC3648300 PMID: 23723920

Abstract

The title ester, C₂₇H₃₀N₂O₃, crystallizes with two independent molecules in the asymmetric unit whose geometrical features are similar. In each molecule, the pyrrolidine ring adopts an envelope conformation, with the fused C atom shared with the piperidine ring as the flap, and the piperidine ring adopts a chair conformation. In the crystal, C—H⋯π interactions link the inversion-related molecules and form a dimeric arrangement in the unit cell.

Related literature

For the superposition of molecules using Qmol, see: Gans & Shalloway (2001 ▶). For ring-puckering parameters, see: Cremer & Pople (1975 ▶). graphic file with name e-69-0o776-scheme1.jpg

Experimental

Crystal data

C₂₇H₃₀N₂O₃
M _r = 430.53
Monoclinic,
a = 22.672 (3) Å
b = 8.8049 (11) Å
c = 24.431 (3) Å
β = 110.487 (2)°
V = 4568.6 (10) Å³
Z = 8
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 292 K
0.22 × 0.20 × 0.18 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
42435 measured reflections
8045 independent reflections
5762 reflections with I > 2σ(I)
R _int = 0.069

Refinement

R[F ² > 2σ(F ²)] = 0.092
wR(F ²) = 0.182
S = 1.18
8045 reflections
583 parameters
H-atom parameters constrained
Δρ_max = 0.43 e Å⁻³
Δρ_min = −0.16 e Å⁻³

Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT (Bruker, 2001 ▶); 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 ▶) and PLATON (Spek, 2009 ▶); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ▶).

Supplementary Material

Click here for additional data file.^{(41.3KB, cif)}

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536813010489/ng5324sup1.cif

e-69-0o776-sup1.cif^{(41.3KB, cif)}

Click here for additional data file.^{(393.6KB, hkl)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813010489/ng5324Isup2.hkl

e-69-0o776-Isup2.hkl^{(393.6KB, hkl)}

Click here for additional data file.^{(9.2KB, cml)}

Supplementary material file. DOI: 10.1107/S1600536813010489/ng5324Isup3.cml

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

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

Cg1 and Cg2 are the centroids of the C19A–C24A and C19B–C24B rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C25A—H25A⋯Cg1ⁱ	0.96	2.81	3.606 (5)	141
C25B—H25F⋯Cg2ⁱⁱ	0.96	2.68	3.495 (5)	143

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

Acknowledgments

SS acknowledges the Department of Science and Technology (DST), India, for providing computing facilities under the DST-Fast Track Scheme. SS also thanks the Vice Chancellor and Management of the Kalasalingam University, Krishnankoil, for their support and encouragement.

supplementary crystallographic information

Comment

In continuation of our work on the crystal structure analyis of pyrrolidine derivatives, we have undertaken the crystal structure determination of the title compound, and the results are presented here.

The X-ray study confirmed the molecular structure and atomic connectivity for (I), as illustrated in Fig. 1. The asymmetric unit of (I) contains two molecules (Fig. 1); their corresponding bond lengths and bond angles are in good agreement. Fig. 2 shows a superposition of the central pyrrolidine ring of both the molecules using Qmol (Gans & Shalloway, 2001); the r.m.s. deviation is 0.012 Å.

The phenyl ring and the first two five membered rings are planar with the maximum deviation of -0.135 (3) and -0.178 (3) Å for atom C16 in molecules A and B, respectively.

The pyrrolidine ring (third five membered ring) is in an envelope conformation, with puckering parameters (Cremer & Pople, 1975) q₂ = 0.464 (3) Å and φ = 73.0 (4) ° for molecule A, and q₂ = 0.455 (4) Å and φ = 75.7 (4) ° for molecule B. Atom C14 deviates 0.697 (3) and 0.697 (2) Å from the least-squares plane through the remaining four atoms (C9/N2/C15/C16) of that of ring in molecules A and B, respectively. The piperidine ring adopts a chair conformation. This is confirmed by the puckering parameters q₂ = 0.028 (3) Å, q₃ = -0.567 (4) Å = Q_T, δ = 177.2 (4)° for molecule A, and q₂ = 0.020 (4) Å, q₃ = -0.569 (4) Å = Q_T, δ = 178.0 (4)° for molecule B.

The molecular structure is influenced by four intramolecular C—H···O close contacts. The crystal packing is stabilized by weak intermolecular C—H···π interactions (Table 1).

Experimental

A mixture of N-alkenyl-3-methyl indole-2-carbaldehyde (1mmol) and pipecolinic acid (1.3mmol) was heated unde Dean-Stark reflux condition for about 12 hours in toluene (10ml) as solvent. The solvent was removed under vacuo. The crude product was subjected to column chromatography using ethyl acetate and hexane as eleuent in 2:1 ratio. Single crystals were grown by slow evaporation from methanol.