11-(4-Methyl­phen­yl)-8,9-dihydro-7H-benzo[f]cyclo­penta­[b]quinolin-10(11H)-one

Cao Yang

doi:10.1107/S1600536812035659

. 2012 Aug 23;68(Pt 9):o2746. doi: 10.1107/S1600536812035659

11-(4-Methylphenyl)-8,9-dihydro-7H-benzo[f]cyclopenta[b]quinolin-10(11H)-one

Cao Yang ^a,^*

PMCID: PMC3435758 PMID: 22969629

Abstract

In the title compound, C₂₃H₁₉NO, the naphthalene ring system and the cyclopent-2-enone ring exhibit planar conformations with maximum deviations of 0.034 (1) and 0.02 (1) Å, respectively. The 1,4-dihydropyridine ring adopts an envelope conformation with the C atom bearing the p-tolyl ring as the flap atom. Intermolecular N—H⋯O hydrogen bonds and C—H⋯π interactions stabilize the crystal packing.

Related literature

For the medicinal use of quinoline and fused quinoline derivatives, see: Audisio et al. (2012 ▶); Kurasawa et al. (2012 ▶); Pokhrel et al. (2012 ▶). For puckering parameters, see: Cremer & Pople (1975 ▶).

Experimental

Crystal data

C₂₃H₁₉NO
M _r = 325.39
Monoclinic,
a = 8.727 (1) Å
b = 11.6820 (14) Å
c = 16.240 (2) Å
β = 98.938 (5)°
V = 1635.5 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 113 K
0.24 × 0.20 × 0.18 mm

Data collection

Rigaku Saturn724 CCD diffractometer
Absorption correction: multi-scan (CrystalClearSM Expert; Rigaku/MSC, 2009 ▶) T _min = 0.981, T _max = 0.986
15928 measured reflections
3899 independent reflections
2991 reflections with I > 2σ(I)
R _int = 0.031

Refinement

R[F ² > 2σ(F ²)] = 0.044
wR(F ²) = 0.124
S = 1.07
3899 reflections
231 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.36 e Å⁻³
Δρ_min = −0.32 e Å⁻³

Data collection: CrystalClearSM Expert (Rigaku/MSC, 2009 ▶); cell refinement: CrystalClearSM Expert; data reduction: CrystalClearSM Expert; 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

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812035659/hg5239sup1.cif

e-68-o2746-sup1.cif^{(20.6KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812035659/hg5239Isup2.hkl

e-68-o2746-Isup2.hkl^{(191.1KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812035659/hg5239Isup3.cml

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

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

Cg1 is the centroid of the C17–C22 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1ⁱ	0.902 (17)	1.983 (17)	2.8519 (13)	161.2 (14)
C15—H15⋯Cg1ⁱⁱ	0.95	3.00	3.8110 (15)	145

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

Acknowledgments

The author is thankful to Professor Youquan Zhu of Nankai University, China, for his kindly help with the collection of the X-ray data set, structure solution and refinement.

supplementary crystallographic information

Comment

Many efforts have been devoted to the synthesis of quinoline and fused quinoline derivaties due to their broad spectrum of bioactivities including anti-norovirus activity (Pokhrel et al. 2012), antikinetoplastid activity (Audisio et al. 2012), antimalarial activity (Kurasawa et al. 2012). These work inspired us to assemble various types of fused quinoline skeletons and evaluate their bioactivities to study the relationship between structure and activity (SAR). Determination of the accurate structure is crucial to do SAR research. During our work on the efficient synthesis and biological study of benzo[f]cyclopenta[b]quinolins, the title compound (I) was isolated and its structure was determined by X-ray diffraction. Herein we report its crystal structure.

In the molecular structure (Fig. 1), the quinoline ring and cyclopent-2-enone ring adopts planar conformations. The atoms with maximal deviation from the the two ring are C9 and ing systr C5 with the distance of 0.034 (1)Å and 0.02 (1) Å, respectively. The dihydropyridine ring is in an envelope (or half boat) conformation, since C1/C2/N1/C4/C5 is coplanar with the largest deviation of 0.040 (1)Å(N1). However, the distance of C3 and the plane consisting of the rest five atoms is 0.212 (1)Å. Cremer & Pople puckering parameters analysis also confirms that the dihydropyridine ring adopts a envelope conformation (Cremer & Pople, 1975). Its puckering amplitude (Q), θ and φ are 0.156 (1)Å, 102.7 (4)° and 0.7 (5)°, respectively. The linkage between p-tolyl and dihydropyridine ring can be described by the torsion angle of C2—C3—C17—C22 (45.46 (15)°) and C4—C3—C17—C22(-76.38 (13)°) respectively. The crystal packing is stabilized by intermolecular N—H···O hydrogen bond and C—H··· π interactions (Fig. 2, Table 1).

Experimental

In a dry 50 mL flask, cyclopentane-1,3-dione (0.10 g, 1 mmol), 4-methylbenzaldehyde (0.12 g, 1 mmol), naphthalen-2-amine (0.14 g,1 mmol), p-toluenesulfonic acid (0.2 g, 1 mmol) and water (10 mL) were mixed and then stirred at 373 K for 5 h. After completion of the reaction, as indicated by TLC, the solid product was collected by filtration and were purified by flash column chromatography (silica gel, mixtures of ethyl acetate / petroleum ether, 1:3, v/v) to afford the desired pure product. m. p.: 562-564 K; IR (KBr,ν, cm^-1): 3165, 3080, 3013, 2962, 1666, 1632, 1584, 1522, 1468, 1397, 1269, 1239, 1220, 1012, 841, 806, 748, 688, 531; ¹H NMR (400 MHz, DMSO-d₆) (δ, ppm): 10.27 (s, 1H, NH), 7.80 (q, J = 8.4 Hz, 3H, ArH), 7.37-7.28 (m, 3H, ArH), 7.05 (d, J = 8.0 Hz, 2H, ArH), 6.94 (d, J = 8.0 Hz, 2H, ArH), 5.58 (s, 1H, CH), 2.71-2.63 (m, 2H, CH₂), 2.34-2.20 (m, 2H, CH₂), 2.14 (s, 3H, CH₃); HRMS (ESI) m/z: Calcd. for C₂₃H₁₉NONa [M+Na]⁺ 348.1364, found: 348.1345.The single-crystal suitable for X-ray diffraction was obtained through slow evaporation of the ethanol solution of the title compound.