Crystal structure of 5′′-(4-chloro­benzyl­idene)-4′-(4-chloro­phen­yl)-1′-methyltri­spiro[acenapthylene-1,2′-pyrrolidine-3′,1′′-cyclo­hexane-3′′,2′′′-[1,3]dioxane]-2(1H),6′′-dione

Kuppan Chandralekha; Deivasigamani Gavaskar; Adukamparai Rajukrishnan Sureshbabu; Srinivasakannan Lakshmi

doi:10.1107/S2056989015018034

. 2015 Oct 3;71(Pt 11):o814–o815. doi: 10.1107/S2056989015018034

Crystal structure of 5′′-(4-chlorobenzylidene)-4′-(4-chlorophenyl)-1′-methyltrispiro[acenapthylene-1,2′-pyrrolidine-3′,1′′-cyclohexane-3′′,2′′′-[1,3]dioxane]-2(1H),6′′-dione

Kuppan Chandralekha ^a, Deivasigamani Gavaskar ^b, Adukamparai Rajukrishnan Sureshbabu ^b, Srinivasakannan Lakshmi ^a,^*

PMCID: PMC4645075 PMID: 26594541

Abstract

In the title compound, C₃₆H₂₉Cl₂NO₄, two spiro links connect the methyl-substituted pyrrolidine ring to the acenaphthylene and cyclohexanone rings. The cyclohexanone ring is further connected to the dioxalane ring by a third spiro junction. The five-membered ring of the acenaphthylen-1-one ring system adopts a flattened envelope conformation, with the ketonic C atom as the flap, whereas the dioxalane and pyrrolidine rings each have a twist conformation. The cyclohexenone ring assumes a boat conformation. An intramolecular C—H⋯O hydrogen-bond interaction is present. In the crystal, molecules are linked by non-classical C—H⋯O hydrogen bonds, forming chains extending parallel to the a axis.

Keywords: crystal structure, spiro pyrrolidines, acenaphthylene, dioxalane, hydrogen bonding

Related literature

For the pharmacological properties of spiro compounds, see: Cravotto et al. (2001 ▸); Raj et al. (2003 ▸); Stylianakis et al. (2003 ▸). For the activities of acenaphthylene derivatives, see: Selvanayagam et al. (2004 ▸); El-Ayaan et al. (2007 ▸); McDavid & Daniels (1951 ▸); El-Ayaan & Abdel-Aziz (2005 ▸); Smith et al. (1979 ▸); Chen et al. (2014 ▸). For the properties and pharmacological activities of dioxalane compounds, see: Narayanasamy et al. (2007 ▸); Küçük et al. (2011 ▸); Shirai et al. (1998 ▸); Bera et al. (2003 ▸); Aepkers & Wünsch (2005 ▸); Ozkanlı et al. (2003 ▸); Liang et al. (2006 ▸).

Experimental

Crystal data

C₃₆H₂₉Cl₂NO₄
M _r = 610.50
Triclinic
a = 8.9791 (4) Å
b = 10.3080 (5) Å
c = 15.7653 (6) Å
α = 88.679 (2)°
β = 83.263 (2)°
γ = 87.408 (2)°
V = 1447.39 (11) Å³
Z = 2
Mo Kα radiation
μ = 0.27 mm⁻¹
T = 293 K
0.35 × 0.30 × 0.25 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2004 ▸) T _min = 0.708, T _max = 0.746
39174 measured reflections
5104 independent reflections
3981 reflections with I > 2σ(I)
R _int = 0.027

Refinement

R[F ² > 2σ(F ²)] = 0.041
wR(F ²) = 0.111
S = 1.06
5104 reflections
389 parameters
H-atom parameters constrained
Δρ_max = 0.47 e Å⁻³
Δρ_min = −0.33 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: SHELXL2014 (Sheldrick, 2015 ▸); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▸) and PLATON (Spek,2009 ▸); software used to prepare material for publication: publCIF (Westrip, 2010 ▸).

Supplementary Material

Crystal structure: contains datablock(s) I. DOI: 10.1107/S2056989015018034/rz5168sup1.cif

e-71-0o814-sup1.cif^{(1.4MB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015018034/rz5168Isup2.hkl

e-71-0o814-Isup2.hkl^{(406.1KB, hkl)}

Click here for additional data file.^{(6.3KB, cml)}

Supporting information file. DOI: 10.1107/S2056989015018034/rz5168Isup3.cml

Click here for additional data file.^{(1.5MB, tif)}

. DOI: 10.1107/S2056989015018034/rz5168fig1.tif

The molecular structure of the title compound, with displacement ellipsoids drawn at the 30% probability level. H atoms are shown as small spheres of arbitary radius.

Click here for additional data file.^{(3.3MB, tif)}

a via . DOI: 10.1107/S2056989015018034/rz5168fig2.tif

Partial crystal packing of the title compound showing the formation of a molecular chain parallel to the a axis via C—H⋯O hydrogen bonds (dashed lines).

CCDC reference: 1427830

Additional supporting information: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (, ).

DHA	DH	HA	D A	DHA
C12H12AO1	0.97	2.27	3.066 (3)	139
C22H24O2ⁱ	0.93	2.35	3.172 (3)	148

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Symmetry code: (i) Inline graphic .

Acknowledgments

The authors thank the single-crystal XRD facility, SAIF IIT Madras, Chennai, for the data collection.

supplementary crystallographic information

S1. Comment

Spiro compounds frequently form a part of pharmacologically relevant alkaloids (Cravatto et al., 2001). Spiro pyrrolidines are an important class of compounds having antibacterial and antifungal activities against human pathogenic bacteria and dermatophytic fungi (Amal Raj et al., 2003), and are active against anti-influenza virus A. (Styliankis et al., 2003). Acenaphthylene derivatives are found to have high κ-opiod receptor affinity and selectivity (Selvanayagam et al., 2004). These derivatives have antitumor (Ayaan et al., 2007), antifungal (McDavid & Daniels, 1951), antimicrobial (Ayaan & Abdel-Aziz, 2005), anti-inflammatory (Smith et al., 1979) and insecticidal activities (Chen et al., 2014). Dioxalane compounds exihibit anti-HIV (Narayanasamy et al., 2007), antibacterial and antifungal (Kucuk et al., 2011), antineoplastic (Shirai et al., 1998), antiviral (Bera et al., 2003), anaesthetic (Aepkers & Wünsch, 2005) and anticonvulsant activities (Ozkanlı et al., 2003). Dioxalane moieties play also a significant role in stabilizing the binding between the mutant HIV-1 RT and nucleoside triphosphate and act as nucleoside reverse transcriptase inhibitors (NRTIs) (Liang et al., 2006).

In the title compound (Fig. 1), the methyl substituted pyrrolidine ring (C7/C8/N/C9/C10/C11), is in twist conformation with puckering parameters q2 = 0.454 (2) Å, φ = 127.8 (3)° .The dioxalane ring (C13/O3/C17/C18/O4) has also a twist conformation (q2 = 0.202 (3) Å, φ = -127.6 (7)°), while the five-membered ring (C10/C26/C27/C32/C33) of the acenaphthylen-1-one ring system adopts a flattened envelope conformation (q2 = 0.112 (2) Å, φ = 26.8 (11)°). The six-membered cyclohexanone ring (C11—C16) adopts a boat conformation (Q_T = 0.690 (2) Å, Θ = 99.72 (16)°, φ = 9.84 (16)°). The least-squares mean plane through the pyrrolidine ring forms dihedral angles of 120 (18), 90.55 (7) and 97.57 (8)° with the mean planes of the attached benzene ring, cyclohexanone ring and cyclopentanone ring, respectively. The mean planes through the cyclohexanone and dioxalane rings form a dihedral angle of 92.61 (10)°. The sum of bond angles around the nitrogen atom of the pyrrolidine ring (338.4°) is in agreement with an sp³ hybridization. The molecular conformation is stabilized by an intramolecular C—H···O hydrogen bond (Table 1). In the crystal (Fig. 2), molecules are linked by weak intermolecular C—H···O hydrogen interactions (Table 1) to form chains extending parallel to the a axis.

S2. Experimental

An equimolar mixture of 7,9-bis[(E)-arylidene-1,4-dioxo-spiro[4,5]decane-8-one (1 mmol), acenapthequinone (1 mmol) and sarcosine in methanol (25-30 ml) was refluxed for 4 hours. After completion of the reaction as indicated by TLC, the solid precipitate was filtered and washed with methanol to give the pure trispiropyrrolidine derivative. Single crystals suitable for the X-ray diffraction analysis were obtained by slow evaporation of the solvent at room temperature.

S3. Refinement

All H atoms were placed in calculated positions, with C—H = 0.93–0.98 Å and refined using a riding-model approximation, with U_iso(H) = 1.2 U_eq(C) or 1.5 U_eq(C) for methyl H atoms. A rotating model was applied to the methyl groups.