6-Chloro-3-[5-(3-meth­oxy-8-methyl-4-quinol­yl)-1-phenyl-4,5-dihydro-1H-pyrazol-3-yl]-2-methyl-4-phenyl­quinoline

Hoong-Kun Fun; Chin Sing Yeap; S Sarveswari; V Vijayakumar; R Prasath

doi:10.1107/S1600536809040252

. 2009 Oct 7;65(Pt 11):o2665–o2666. doi: 10.1107/S1600536809040252

6-Chloro-3-[5-(3-methoxy-8-methyl-4-quinolyl)-1-phenyl-4,5-dihydro-1H-pyrazol-3-yl]-2-methyl-4-phenylquinoline

Hoong-Kun Fun ^a,^*,^‡, Chin Sing Yeap ^a,^§, S Sarveswari ^b, V Vijayakumar ^b, R Prasath ^b

PMCID: PMC2971305 PMID: 21578276

Abstract

In the title compound, C₃₆H₂₉ClN₄O, the dihydropyrazole ring adopts an envelope conformation. The two quinoline ring systems (r.m.s. deviations = 0.029 and 0.018 Å) are oriented at a dihedral angle of 71.43 (4)°. One of the quinoline rings makes a dihedral angle of 65.40 (7)° with the phenyl substituent. In the crystal, molecules are linked into chains along the b axis by intermolecular C—H⋯N hydrogen bonds. In addition, C—H⋯π and π–π [centroid–centroid distance = 3.7325 (8) Å] interactions are observed.

Related literature

For general background to quinoline and its derivatives, see: Morimoto et al. (1991 ▶); Michael (1997 ▶); Markees et al. (1970 ▶); Campbell et al. (1988 ▶). For applications of quinolines, see: Maguire et al. (1994 ▶); Kalluraya & Sreenivasa (1998 ▶); Roma et al. (2000 ▶); Chen et al. (2001 ▶); Skraup (1880 ▶). For the synthesis of quinoline derivatives, see: Katritzky & Arend (1998 ▶); Jiang & Si (2002 ▶). For ring conformations, see: Cremer & Pople (1975 ▶). For the stability of the temperature controller used for the data collection, see: Cosier & Glazer (1986 ▶).

Experimental

Crystal data

C₃₆H₂₉ClN₄O
M _r = 569.08
Monoclinic,
a = 14.1209 (3) Å
b = 20.2273 (4) Å
c = 10.1892 (2) Å
β = 95.358 (1)°
V = 2897.6 (1) Å³
Z = 4
Mo Kα radiation
μ = 0.17 mm⁻¹
T = 100 K
0.65 × 0.45 × 0.22 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.899, T _max = 0.964
57308 measured reflections
10615 independent reflections
8632 reflections with I > 2σ(I)
R _int = 0.032

Refinement

R[F ² > 2σ(F ²)] = 0.056
wR(F ²) = 0.135
S = 1.08
10615 reflections
495 parameters
All H-atom parameters refined
Δρ_max = 0.52 e Å⁻³
Δρ_min = −0.38 e Å⁻³

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT (Bruker, 2005 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809040252/ci2931sup1.cif

e-65-o2665-sup1.cif^{(29.1KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809040252/ci2931Isup2.hkl

e-65-o2665-Isup2.hkl^{(519.1KB, 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
C13—H13⋯N1ⁱ	0.95 (2)	2.56 (2)	3.410 (2)	149 (2)
C14—H14⋯Cg1	1.00 (2)	2.92 (2)	3.685 (2)	134 (2)
C17—H17A⋯Cg2ⁱⁱ	0.97 (2)	2.55 (2)	3.5018 (14)	169 (1)
C25—H25⋯Cg3ⁱⁱⁱ	0.96 (2)	2.79 (2)	3.7359 (17)	169 (2)

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) . Cg1, Cg2 and Cg3 are centroids of the C21–C26, N1/C1/C6–C9 and C28–C33 benzene rings, respectively.

Acknowledgments

HKF thanks Universiti Sains Malaysia (USM) for the Research University Golden Goose grant No. 1001/PFIZIK/811012. CSY thanks USM for the award of a USM Fellowship. VV is grateful to DST-India for funding through the Young Scientist Scheme (Fast Track Proposal).

supplementary crystallographic information

Comment

Quinoline and its derivatives are very important compounds because of their wide occurrence in natural products (Morimoto et al., 1991; Michael, 1997) and biologically active compounds (Markees et al., 1970; Campbell et al., 1988). A large variety of quinolines have interesting physiological activities and found attractive applications as pharmaceuticals, agrochemicals and as synthetic building blocks (Maguire et al., 1994; Kalluraya & Sreenivasa, 1998; Roma et al., 2000; Chen et al., 2001; Skraup, 1880). Many synthetic methods such as Skraup, Doebner-Von Miller, Friedländer and Combes reactions have been developed for the preparation of quinolines, but due to their great importance, the synthesis of new derivatives of quinoline remains an active research area (Katritzky & Arend, 1998; Jiang & Si, 2002).

The title compound consists of two phenyl rings, two quinoline rings and a 4,5-dihydropyrazole ring (Fig. 1). The 4,5-dihydropyrazole ring (N2/N3/C16–C18) adopts an envelope conformation with C18 as the flap atom, and with puckering amplitude Q = 0.2121 (14) Å and φ = 256.8 (3)° (Cremer & Pople, 1975). The N1/C1–C9 quinoline ring is planar with a maximum deviation of 0.046 (1) Å for atom C8 and in the N4/C19–C27 ring atom C19 deviates a maximum of 0.034 (1) Å. The two quinoline rings (N1/C1–C9 and N4/C19–C27) are oriented at angle of 71.43 (4)°. The C10–C15 benzene ring makes a dihedral angle of 65.40 (7)° with the N1/C1–C9 quinoline ring.

In the crystal structure, molecules are linked into chains along the b axis (Fig. 2) by intermolecular C13—H13···N1 hydrogen bonds (Table 1). In addition, the structure is stabilized by the C—H···π (Table 1) and π···π interactions [Cg1···Cg1^iv = 3.7325 (8) Å; Cg1 is centroid of C21–C26 ring; (iv) 1 - x, 1 - y, -z].

Experimental

A mixture of 1-(6-chloro-2-methyl-4-phenylquinolin-3-yl)-3- (2-chloroquinolin-2-yl)prop-2-en-1-one (0.468 g, 0.001 M) and phenyl hydrazine in (0.756 g, 0.007 M) in distilled methanol was refluxed for 8 h and the resulting mixture was concentrated to remove the methanol and then poured onto ice and neutralized with dilute HCl. The resultant solid was filtered, dried and purified by column chromatography using 1:1 mixture of chloroform and petroleum ether. The resultant product was recrystallized from methanol (m.p. 456–458 K).