Crystal structure of 15-(2-chloro­phen­yl)-6b-hy­droxy-17-methyl-6b,7,16,17-tetra­hydro-7,14a-methanona­phtho[1′,8′:1,2,3]pyrrolo­[3′,2′:8,8a]azuleno[5,6-b]quinolin-14(15H)-one

J M Joseph; Vijayan Viswanathan; Devadasan Velmurugan

doi:10.1107/S2056989015024767

. 2015 Dec 31;71(Pt 12):o1091–o1092. doi: 10.1107/S2056989015024767

Crystal structure of 15-(2-chlorophenyl)-6b-hydroxy-17-methyl-6b,7,16,17-tetrahydro-7,14a-methanonaphtho[1′,8′:1,2,3]pyrrolo[3′,2′:8,8a]azuleno[5,6-b]quinolin-14(15H)-one

J M Joseph ^a, Vijayan Viswanathan ^a, Devadasan Velmurugan ^a,^*

PMCID: PMC4719995 PMID: 26870514

Abstract

In the title compound, C₃₄H₂₅ClN₂O₂, the fused pyrrolidine ring adopts an envelope conformation with the N atom as the flap. The two adjacent cyclopentane rings also adopt envelope conformations. The mean plane of the pyrrolidine ring makes dihedral angles of 40.53 (10) and 80.23 (10)° with the mean planes of the cyclopentane rings. The dihedral angle between the mean planes of the cyclopentane rings is 46.71 (9)°. An intramolecular O—H⋯N hydrogen bond is observed. In the crystal, molecules are linked by C—H⋯O, C—H⋯N and C—H⋯π interactions, forming a layer parallel to (10-2).

Keywords: crystal structure, pyrrolidine derivative, hydrogen bonding

Related literature

For biological activities of pyrrolidine derivatives, see: Aravindan et al. (2004 ▸); Gayathri et al. (2005 ▸); Seki et al. (2013 ▸); Li & Xu (2004 ▸); Arun et al. (2014 ▸); Govind et al. (2003 ▸); Nirmala et al. (2009 ▸); Sharma & Soman (2015 ▸); Bellina & Rossi (2006 ▸); Babu et al. (2012 ▸). For related structures, see: Savithri et al. (2014 ▸). graphic file with name e-71-o1091-scheme1.jpg

Experimental

Crystal data

C₃₄H₂₅ClN₂O₂
M _r = 529.01
Monoclinic,
a = 11.1328 (2) Å
b = 13.0756 (3) Å
c = 19.0866 (4) Å
β = 103.738 (1)°
V = 2698.91 (10) Å³
Z = 4
Mo Kα radiation
μ = 0.18 mm⁻¹
T = 293 K
0.30 × 0.25 × 0.20 mm

Data collection

Bruker SMART APEXII area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2008 ▸) T _min = 0.949, T _max = 0.966
25834 measured reflections
6713 independent reflections
4796 reflections with I > 2σ(I)
R _int = 0.022

Refinement

R[F ² > 2σ(F ²)] = 0.049
wR(F ²) = 0.139
S = 1.05
6713 reflections
354 parameters
H-atom parameters constrained
Δρ_max = 0.40 e Å⁻³
Δρ_min = −0.58 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: SHELXL2014 (Sheldrick, 2015 ▸); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▸); software used to prepare material for publication: PLATON (Spek, 2009 ▸).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989015024767/is5437sup1.cif

e-71-o1091-sup1.cif^{(787KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015024767/is5437Isup2.hkl

e-71-o1091-Isup2.hkl^{(533.5KB, hkl)}

Click here for additional data file.^{(1.4MB, tif)}

. DOI: 10.1107/S2056989015024767/is5437fig1.tif

The molecular structure of the title compound, showing the atomic numbering and displacement ellipsoids drawn at 20% probability level.

Click here for additional data file.^{(1.4MB, tif)}

c . DOI: 10.1107/S2056989015024767/is5437fig2.tif

A packing diagram of the title compound viewed approximately down the c axis, showing the Inline graphic (14) ring motif formed by C—H⋯N hydrogen bonds (dashed lines). H-atoms not involved in hydrogen bonds have been excluded for clarity.

Click here for additional data file.^{(1.2MB, tif)}

b . DOI: 10.1107/S2056989015024767/is5437fig3.tif

A packing diagram of the title compound viewed approximately down the b axis. C—H⋯O hydrogen bonds are indicated by dashed lines. H atoms not involved in the hydrogen bonds have been excluded for clarity.

Click here for additional data file.^{(1.1MB, tif)}

. DOI: 10.1107/S2056989015024767/is5437fig4.tif

A packing diagram of the title compound showing a C—H⋯π interaction (dashed line).

CCDC reference: 1444162

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

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

Cg1 is the centroid of the N1/C1/C6–C9 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2A⋯N2	0.82	2.12	2.664 (2)	124
C25—H25⋯N1ⁱ	0.93	2.59	3.503 (2)	169
C33—H33⋯O1ⁱⁱ	0.93	2.40	3.212 (3)	146
C17—H17⋯Cg1ⁱⁱⁱ	0.93	2.73	3.553 (3)	147

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

Acknowledgments

The authors thank the TBI X-ray facility, CAS in Crystallography and Biophysics, University of Madras, India, for the data collection.

supplementary crystallographic information

S1. Comment

Pyrrolidine compounds are often encountered in pharmacologically relevant alkaloids (Aravindan et al., 2004). Optically active pyrrolidines have been used as intermediates, chiral ligands or auxiliaries in controlled asymmetric synthesis (Savithri et al., 2014). Synthetic spiro pyrrolidine derivatives exhibit activity against the aldose reductase enzyme, which controls influenza virus (Gayathri et al., 2005) and also pyrrolidine compounds are reported to exhibit ischemic stroke (Seki et al., 2013), anti-inflammatory (Li & Xu, 2004), antitumor (Arun et al., 2014), antimicrobial, antifungal (Govind et al., 2003), antibiotic (Nirmala et al., 2009) and anti-diabetic (Sharma & Soman, 2015) activities and inhibition of retroviral reverse transcriptases [i.e., human immunodeficiency virus type 1 (HIV-1)], cellular DNA polymerases and protein kinases (Bellina & Rossi, 2006). They are also anticonvulsants, sphingosine-1-phosphate (S1P) receptor agonists, malic enzyme inhibitors, ketoamide-based cathepsin K inhibitors and human melanocortin-4 receptor agonists (Babu et al., 2012). In view of the above biological importance, the crystal structure of the title compound was determined.

In the title molecule, one cyclopentane ring I (C10–C12/C22/C23) is fused with the other cyclopentane ring II (C22–C24/C29/C30) of the acenaphthylene ring system (C22–C33). The pyrrolidine ring (C12/C14/C21/N2/C22) is fused with the cyclopentane ring I, and adopts an envelope conformation with atom N2 as the flap atom deviating by 0.5765 (2) Å from the mean plane defined by the other atoms (C12/C14/C21/C22). The two cyclopentane rings I and II adopt envelope conformations with atoms C11 and C22 as the flap atoms, respectively, deviating by 0.7033 and 0.1765 Å from the mean plane. The mean plane of the pyrrolidine ring makes dihedral angles of 40.53 (10) and 80.23 (10)° with the mean planes of the cyclopentane rings I and II, respectively. The mean plane of the pyrrolidine ring makes dihedral angles of 82.04 (8) and 68.25 (9)° with the mean plane of the acenapthylene and phenyl (C8–C13) ring systems, respectively. The mean plane of the cyclopentane ring I makes a dihedral angle of 46.71 (9)° with the mean plane of the cyclopentane ring II. The mean plane of the cyclopentane ring makes dihedral angles of 47.85 (7) and 87.06 (9)° with the mean plane of the acenaphthylene ring system and the phenyl ring, respectively.

In the crystal, a pair of C—H···N interactions (Table 1) show an R₂²(14) ring (Fig. 2). In addition, a C—H···O hydrogen bond links the symmetry-related molecules, forming a helical chain running along the b axis (Fig. 3). The two molecules are also held together by a C—H···π interaction (Fig. 4).

S2. Experimental

A mixture of (E)-2-(2-chlorobenzylidene)-3,4-dihydroacridin-1(2H)-one (1 mmol), acenaphthoquinone (1 mmol) and sarcosine (1.5 mmol) was heated to reflux in toluene (3 ml) for 10 h. After completion of the reaction as evident from TLC, the reaction mixture was extracted with ethyl acetate (2 × 20 ml), washed with water (2 × 10 ml), dried over anhydrous Na₂SO₄ and concentrated under reduced pressure, subjected to column chromatography using petroleum ether-AcOEt (5:1 v/v) as eluent to obtain pure product. Single crystals suitable for X-ray diffraction were prepared by slow evaporation of a solution of the title compound in ethanol at room temperature.