9-(Thio­phen-2-yl)-8,9-dihydro-3H-pyrazolo­[4,3-f]quinolin-7(6H)-one ethanol monosolvate

Juhua Peng; Runhong Jia

doi:10.1107/S1600536812033533

. 2012 Aug 1;68(Pt 9):o2608. doi: 10.1107/S1600536812033533

9-(Thiophen-2-yl)-8,9-dihydro-3H-pyrazolo[4,3-f]quinolin-7(6H)-one ethanol monosolvate

Juhua Peng ^a,^*, Runhong Jia ^a

PMCID: PMC3435639 PMID: 22969512

Abstract

In the title compound, C₁₄H₁₁N₃OS·C₂H₅OH, the dihedral angle between the pyridine N—C_fused—C_fused—C(thiophene) plane and the plane of the thiophene ring is 81.9 (3)°, indicating that they are close to perpendicular. The dihedral angle between this pyridine plane and the benzene ring is 1.3 (3)°. The thiophene ring is disordered over two coplanar orientations with an occupancy ratio of 0.692 (7):0.308 (7), while the ethanol solvent molecule is also disordered over two sets of site in a 0.66 (4):0.34 (4) ratio. In the crystal, chains are formed along the b axis by N—H⋯O and O—H⋯N interactions with adjacent chains being connected through C—H⋯N and C—H⋯S interactions.

Related literature

For background to the biological activity of quinolinone derivatives, see: Larsen et al. (1996 ▶); Chackal et al. (2002 ▶); Kalluraya & Sreenivasa (1998 ▶); Xu et al. (2000 ▶). For the synthesis of quinolinones, see: Suarez et al. (1999 ▶).

Experimental

Crystal data

C₁₄H₁₁N₃OS·C₂H₆O
M _r = 315.39
Monoclinic,
a = 9.3831 (10) Å
b = 19.138 (2) Å
c = 8.7490 (9) Å
β = 99.412 (1)°
V = 1549.9 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.22 mm⁻¹
T = 298 K
0.38 × 0.19 × 0.12 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.921, T _max = 0.974
7663 measured reflections
2707 independent reflections
1526 reflections with I > 2σ(I)
R _int = 0.041

Refinement

R[F ² > 2σ(F ²)] = 0.052
wR(F ²) = 0.154
S = 1.02
2707 reflections
248 parameters
?
Δρ_max = 0.28 e Å⁻³
Δρ_min = −0.26 e Å⁻³

Data collection: SMART (Bruker, 1998 ▶); cell refinement: SAINT (Bruker, 1999 ▶); 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

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812033533/zq2174sup1.cif

e-68-o2608-sup1.cif^{(21.9KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812033533/zq2174Isup2.hkl

e-68-o2608-Isup2.hkl^{(133KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812033533/zq2174Isup3.cml

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
N1—H1⋯O2ⁱ	0.86	1.99	2.838 (16)	170
N3—H3⋯O1ⁱⁱ	0.86	2.04	2.863 (4)	160
O2—H2⋯N2	0.82	2.05	2.855 (14)	167
C8—H8⋯S1ⁱⁱⁱ	0.98	2.86	3.802 (6)	162
C9—H9A⋯N1ⁱⁱⁱ	0.97	2.56	3.529 (7)	175

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

Acknowledgments

The authors thank the National Science Foundation of China (No. 20672090) for financial support.

supplementary crystallographic information

Comment

The quinoline ring system is an important structural unit widely existing in alkaloids, therapeutics and synthetic analogues with interesting biological activities (Larsen et al., 1996). A large variety of quinoline derivatives have been used as antimalarial, anti-inflammatory, antiasthmatic, antibacterial, antihypertensive and tyrokinase PDGF-RTK inhibiting agents (Kalluraya & Sreenivasa, 1998). Various quinolinone derivatives are known to display interesting biological properties, for example, quinolinones represent the structural basis of many biologically active compounds, such as those with cardiovascular, anti-osteoporosis, anti-tumor (Chackal et al., 2002), antiinflammatory, and anti-virus (Xu et al., 2000) activities and so on.

Due to their diverse ranges of biological properties, the synthesis of these important molecules has attracted widespread attention. Some researchers have reported the synthesis of quinolinones (Suarez et al., 1999). To the best of our knowledge, however, the pyrazolo[4,3-f]quinolin-7-one derivatives have not been investigated. Because of the biological activities they exhibit, these compounds have distinguished themselves as heterocycles of profound chemical and biological significance.

In this paper we report the crystal structure of the title compound, C₁₄H₁₁N₃O_S.C₂H₆O, which was synthesized by the reaction of thiophene-2-carbaldehyde, 2,2-dimethyl-1,3-dioxane-4,6-dione, and indazol-5-amine in ethylene glycol without catalyst under microwave irradiation.

In the crystal structure of the title compound, the pyridine ring exhibits an envelope-like structure. The dihedral angle between the pyridine C6/C7/C8/N3 plane and the C11/C12/C13/C14/S1 thiophene ring is 81.9 (3)°, indicating that they are close to perpendicular. The dihedral angle between the pyridine C6/C7/C8/N3 plane and the C2—C7 benzene ring is 1.3 (3)°. The thiophene ring is disordered over two coplanar orientations with an occupancy ratio of 0.692 (7):0.308 (7) while the ethanol solvent molecule is also disordered over two sets of positions with a ratio of 0.66 (4):0.34 (4). Chains are formed along the b axis by N-H···O and O-H···N interactions and adjacent chains are connected through C-H···N and C-H···S interactions.

Experimental

The title compound was prepared by the reaction of thiophene-2-carbaldehyde (1 mmol), 2,2-dimethyl-1,3-dioxane-4,6-dione (1 mmol), and indazol-5-amine (1 mmol) in ethylene glycol (1.0 ml). Single crystals were obtained by slow evaporation of a 95% aqueous ethanol solution (yield 70%; m.p. 553–554 K).

IR (cm^-1): 3194, 3013, 2967, 1681, 1502, 1390, 1241, 1162, 1049, 937, 843, 704. ¹H NMR (DMSO-d₆): 13.03 (s, 1H, NH), 10.21 (s, 1H, NH), 7.42 (d, J = 8.8 Hz, 1H, ArH), 7.31–7.30 (m, 1H, ArH), 7.02 (d, J = 8.8 Hz, 1H, ArH), 6.92–6.87 (m, 2H, ArH), 4.98 (d, J = 4.4 Hz, 1H, CH), 3.12–3.06 (m, 1H, CH₂), 2.77–2.72 (m, 1H, CH₂).