4′-Methyl-14′,19′-dioxa-4′-aza­spiro­[acenaphthyl­ene-1,5′-tetra­cyclo­[18.4.0.02,6.08,13]tetra­cosa­ne]-1′(24′),8′,10′,12′,20′,22′-hexa­ene-2,7′(1H)-dione

Sibi Narayanan; Thothadri Srinivasan; Santhanagopalan Purushothaman; Raghavachary Raghunathan; Devadasan Velmurugan

doi:10.1107/S1600536812046144

. 2012 Nov 14;68(Pt 12):o3345. doi: 10.1107/S1600536812046144

4′-Methyl-14′,19′-dioxa-4′-azaspiro[acenaphthylene-1,5′-tetracyclo[18.4.0.0^2,6.0^8,13]tetracosane]-1′(24′),8′,10′,12′,20′,22′-hexaene-2,7′(1H)-dione

Sibi Narayanan ^a, Thothadri Srinivasan ^a, Santhanagopalan Purushothaman ^b, Raghavachary Raghunathan ^b, Devadasan Velmurugan ^a,^*

PMCID: PMC3588946 PMID: 23476182

Abstract

In the title compound, C₃₃H₂₉NO₄, the acenaphthylene ring system is essentially planar (r.m.s. deviation = 0.0290 Å). The pyrrolidine ring adopts a C-envelope conformation with a C atom displaced by 0.671 (2) Å from the mean-plane formed by the remaining ring atoms. The pyrrolidine ring is fused to acenaphthylene ring system making a dihedral angle of 88.0 (7)°. In the crystal, molecules are linked into R ² ₂(9) dimers via C—H⋯N and C—H⋯O hydrogen bonds. Two C atoms act as donors to the same O atom acceptor, resulting in the formation of R ² ₁(7) ring motifs. These two motifs combine to form hydrogen-bonded sheets running along the a- and b-axis directions.

Related literature

For background to natural and synthetic pharmacologically active pyrrolidines, see: Waldmann (1995 ▶). For related structures, see: Augustine et al. (2010 ▶); Narayanan et al. (2012 ▶). For graph-set motifs, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C₃₃H₂₉NO₄
M _r = 503.57
Monoclinic,
a = 11.248 (2) Å
b = 16.609 (3) Å
c = 14.037 (3) Å
β = 92.965 (6)°
V = 2618.8 (9) Å³
Z = 4
Mo Kα radiation
μ = 0.08 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
24740 measured reflections
6363 independent reflections
4183 reflections with I > 2σ(I)
R _int = 0.035

Refinement

R[F ² > 2σ(F ²)] = 0.045
wR(F ²) = 0.128
S = 1.01
6363 reflections
345 parameters
H-atom parameters constrained
Δρ_max = 0.22 e Å⁻³
Δρ_min = −0.21 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 (Farrugia, 2012 ▶); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ▶).

Supplementary Material

Click here for additional data file.^{(27.4KB, cif)}

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812046144/pv2602sup1.cif

e-68-o3345-sup1.cif^{(27.4KB, cif)}

Click here for additional data file.^{(305.2KB, hkl)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812046144/pv2602Isup2.hkl

e-68-o3345-Isup2.hkl^{(305.2KB, 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
C9—H9⋯N1ⁱ	0.93	2.62	3.535 (3)	167
C15—H15⋯O1ⁱ	0.93	2.50	3.414 (2)	168
C27—H27B⋯O2ⁱⁱ	0.97	2.48	3.403 (2)	158
C29—H29⋯O2ⁱⁱ	0.93	2.57	3.450 (2)	159

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

Acknowledgments

The authors thank the TBI X-ray facility, CAS in Crystallography and Biophysics, University of Madras, India, for the data collection. SN thanks the University Grant Commission (UGC), Government of India, New Delhi, for a Meritorious Fellowship under the SAP programme.

supplementary crystallographic information

Comment

Highly functionalized pyrrolidines have gained much interest in the past few years as they constitute the main structural element of many natural and synthetic pharmacologically active compounds (Waldmann, 1995). In continuation of our work on the crystal structure analysis of spiro-pyrrolidine derivatives (Narayanan et al., 2012), the crystal structure of the title compound has been carried out and the results are presented here.

The bond lengths and angles in the title molecule (Fig. 1) are within normal ranges and comparable to those found in closely related structures (Narayanan et al., 2012; Augustine et al., 2010). The acenaphthylene ring system (C4–C15) is essentially planar (rmsd 0.0290 Å). The pyrrolidine ring (C1–C4/N1) adopts a C4-envelop conformation with C4 0.671 (2) Å displaced from the mean-plane formed by the remaining ring atoms. The pyrrolidine ring is fused to acenaphthylene ring system; the dihedral angle between these two ring systems being 88.0 (7)°.

The molecules are linked into dimers via C9—H9···N1 and C15—H15···O1 hydrogen bonds with the graph-set motif R²₂(9) (Bernstein et al., 1995). Similarly, atoms C27 and C29 act as donors to form bifurcated hydrogen bonds with atom O2 as an acceptor, resulting in the formation of R²₁(7) ring motif. These two motifs combine to form a hydrogen-bonded molecular ribbons running along the a and b-axes.

Experimental

A mixture of acenaphthylene-1,2-dione (182 mg, 1 mmol), sarcosine (90 mg, 1 mmol) and (4E)-12,17-dioxatricyclo[16.4.0.0^6,11]docosa -1(22),4,6,8,10,18,20-heptaen-3-one (300 mg 1.0 mmol) in toluene (20 ml) was refluxed under Dean-Stark reaction condition until the disappearance of starting materials as evidenced by TLC. The reaction mixture was concentrated in vacuo and extracted with water (50 ml) and dichloromethane (2x50 ml). The organic layer was washed with brine solution, dried with anhydrous sodium sulfate and concentrated in vacuo. The residue was purified by column chromatography with hexane-ethylacetate (9:1) mixture to yield macrocycle in good yields. The product was dissolved in chloroform and heated for two minutes. The resulting solution was subjected to crystallization by slow evaporation of the solvent resulting in single crystals suitable for XRD studies.