3′′-(2-Fluoro­benzyl­idene)-4′-(2-fluoro­phen­yl)-1′-methyl­dispiro­[acenaphthyl­ene-1,2′-pyrrolidine-3′,1′′-cyclo­penta­ne]-2,2′′-dione

Gao-Zhi Chen; Xiao-Yan Wei; Yi Wang; Lu-Qing Ren; Xiao-Kun Li

doi:10.1107/S1600536812051550

. 2013 Jan 19;69(Pt 2):o249–o250. doi: 10.1107/S1600536812051550

3′′-(2-Fluorobenzylidene)-4′-(2-fluorophenyl)-1′-methyldispiro[acenaphthylene-1,2′-pyrrolidine-3′,1′′-cyclopentane]-2,2′′-dione

Gao-Zhi Chen ^a, Xiao-Yan Wei ^a, Yi Wang ^a, Lu-Qing Ren ^a, Xiao-Kun Li ^a,^*

PMCID: PMC3569782 PMID: 23424528

Abstract

In the title compound, C₃₃H₂₅F₂NO₂, the acenaphthene ring system forms dihedral angles of 50.93 (14) and 36.89 (14)° with the benzene rings. The pyrrolidine and cyclopentanone rings adopt envelope (with the N atom as the flap) and twisted conformations, respectively. In the crystal, C—H⋯O and C—H⋯F interactions link the molecules.

Related literature

For related structures, see: Abdul Ajees et al. (2002 ▶); Usha et al. (2003 ▶). For background to the biological properties of spiro-pyrrolidine derivatives, see: Chande et al. (2005 ▶); Dandia et al. (2003 ▶); Cravotto et al. (2001 ▶); Winfred et al. (2000 ▶); Metwally et al. (1998 ▶); Suenaga et al. (2001 ▶). For the synthesis of the title compound, see: Kumar et al. (2008a ▶,b ▶); Liang et al. (2009 ▶).

Experimental

Crystal data

C₃₃H₂₅F₂NO₂
M _r = 505.54
Orthorhombic,
a = 17.728 (13) Å
b = 12.272 (9) Å
c = 12.094 (8) Å
V = 2631 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 293 K
0.45 × 0.38 × 0.27 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2002 ▶) T _min = 0.641, T _max = 1.000
12188 measured reflections
2500 independent reflections
2072 reflections with I > 2σ(I)
R _int = 0.123

Refinement

R[F ² > 2σ(F ²)] = 0.055
wR(F ²) = 0.126
S = 1.02
2500 reflections
344 parameters
13 restraints
H-atom parameters constrained
Δρ_max = 0.24 e Å⁻³
Δρ_min = −0.32 e Å⁻³

Data collection: SMART (Bruker, 2002 ▶); cell refinement: SAINT (Bruker, 2002 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Click here for additional data file.^{(26.1KB, cif)}

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812051550/pk2458sup1.cif

e-69-0o249-sup1.cif^{(26.1KB, cif)}

Click here for additional data file.^{(125.3KB, hkl)}

Structure factors: contains datablock(s) cd20184. DOI: 10.1107/S1600536812051550/pk2458Isup2.hkl

e-69-0o249-Isup2.hkl^{(125.3KB, 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—H3B⋯O1ⁱ	0.97	2.35	3.317 (5)	172
C14—H14A⋯F2ⁱⁱ	0.93	2.43	3.212 (7)	141
C25—H25⋯O2ⁱⁱⁱ	0.93	2.58	3.458 (7)	158

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

Acknowledgments

This work was supported by the Zhejiang Provincial Natural Science Foundation of China (grant Nos. LY12H16003 and Y4110197) and the Project of Wenzhou Science & Technology Bureau (Y20100273). The X-ray crystallographic facility at the Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, is gratefully acknowledged for the data collection.

supplementary crystallographic information

Comment

Spiro-pyrrolidine compounds find applications in the synthesis of biologically active compounds. The synthesis of spiro compounds has drawn considerable attention of chemists, in view of their wide spectrum of pharmacological properties (Chande et al., 2005; Dandia et al., 2003; Cravotto et al., 2001; Winfred et al., 2000; Metwally et al., 1998; Suenaga et al., 2001). In the present study, the 1,3-dipolar cycloaddition of an azomethine ylide generated in situ from acenaphthenequinone and sarcosine to novel mono-carbonyl analogue of curcumin containg cyclopentanone afforded the title compound (Kumar et al., 2008; Liang et al., 2009). With this background, and in continuation of our structural analysis of spiro-pyrrolidine derivatives, the X-ray crystal structure determination of the title compound, (I), was undertaken.

The bond lengths and angles in the pyrrolidine ring are slightly larger than normal values because of bulky substituents on the pyrrolidine moiety. A similar effect has been observed in related reported structures (Abdul Ajees et al., 2002; Usha et al., 2003). The sum of the angles at atom N1 [339.1 (11)°] is in accordance with sp³-hybridization. The dihedral angles between the acenaphthene ring system and phenyl rings C21—C26 and C27—C32 are 50.93 (14)° and 36.89 (14)° respectively, while that between the two phenyl-ring substituents is 87.55 (17)°. The pyrrolidine and cyclopentanone ring both adopt an envelope conformation. In addition to van der Waals interactions, the crystal structure is stabilized by C—H···O and C—H···F intramolecular interactions. In the present study, the 1,3-dipolar cycloaddition of an azomethine ylide generated in situ from acenaphthenequinone and sarcosine to novel mono-carbonyl analogue of curcumin containg cyclopentanone afforded title compound.

Experimental

A mixture of (2E,5E)-2,5-bis(2-fluorobenzylidene)cyclopentanone (1 mmol), (Liang et al., 2009), acenaphthenequinone (0.182 g, 1 mmol), and sarcosine (0.089 g, 1 mmol) was dissolved in methanol (10 mL) and refluxed for 1 h. After completion of the reaction as evident from TLC, the mixture was cooled to room temperature and poured into cold water (50 mL). The precipitate was filtered and washed with water to obtain pure product as a yellow solid (79.6% yield, mp 93.2–95.0°C). Single crystals were grown in an ethyl acetate/CH₂Cl₂ mixture (2:1ν/ν).