3-Hy­droxy-1-methyl-2-[4-(piperidin-1-yl)phen­yl]quinolin-4(1H)-one

Michał Wera; Vasyl G Pivovarenko; Artur Sikorski; Tadeusz Lis; Jerzy Błażejowski

doi:10.1107/S1600536811005046

. 2011 Feb 19;67(Pt 3):o654. doi: 10.1107/S1600536811005046

3-Hydroxy-1-methyl-2-[4-(piperidin-1-yl)phenyl]quinolin-4(1H)-one

Michał Wera ^a, Vasyl G Pivovarenko ^b, Artur Sikorski ^a, Tadeusz Lis ^c, Jerzy Błażejowski ^a,^*

PMCID: PMC3051995 PMID: 21522406

Abstract

There are two structurally similar but crystallographically independent molecules (A and B) in the asymmetric unit of the title compound, C₂₁H₂₂N₂O₂, which are linked via two O—H⋯O hydrogen bonds. An intramolecular O—H⋯O hydrogen bond also occurs in each molecule. In the crystal, the A and B molecules are further linked through C—H⋯O interactions. The benzene ring is twisted at an angle of 69.9 (1) and 83.4 (1)° relative to the 1,4-dihydroquinoline skeleton in molecules A and B, respectively. Adjacent 1,4-dihydroquinoline units of molecules A are parallel, while molecules A and B are oriented at an angle of 32.8 (1)°.

Related literature

For general background to quinolin-4(1H)-ones, see: Bilokin’ et al. (2009) ▶; Mitscher (2005 ▶); Yushchenko et al. (2007 ▶); Sengupta & Kasha (1979 ▶). For related structures, see: Czaun et al. (2002 ▶); Mphahlele et al. (2002 ▶); Mphahlele & El-Nahas (2004 ▶). For intermolecular interactions, see: Aakeröy et al. (1992 ▶); Novoa et al. (2006 ▶). For the synthesis, see: Hradil et al. (1999) ▶; Yushchenko et al. (2006 ▶).

Experimental

Crystal data

C₂₁H₂₂N₂O₂
M _r = 334.41
Monoclinic,
a = 9.621 (4) Å
b = 18.622 (6) Å
c = 18.955 (7) Å
β = 104.17 (3)°
V = 3293 (2) Å³
Z = 8
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 180 K
0.40 × 0.35 × 0.30 mm

Data collection

Oxford Diffraction Xcalibur PX diffractometer with a CCD area detector
41668 measured reflections
13682 independent reflections
6901 reflections with I > 2σ(I)
R _int = 0.040

Refinement

R[F ² > 2σ(F ²)] = 0.059
wR(F ²) = 0.133
S = 1.01
13682 reflections
455 parameters
H-atom parameters constrained
Δρ_max = 0.50 e Å⁻³
Δρ_min = −0.25 e Å⁻³

Data collection: CrysAlis CCD (Oxford Diffraction, 2003 ▶); cell refinement: CrysAlis RED (Oxford Diffraction, 2003 ▶); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811005046/om2406sup1.cif

e-67-0o654-sup1.cif^{(33.3KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811005046/om2406Isup2.hkl

e-67-0o654-Isup2.hkl^{(668.8KB, 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
O11A—H11A⋯O12A	0.84	2.32	2.760 (2)	113
O11A—H11A⋯O12B	0.84	1.95	2.723 (2)	153
O11B—H11B⋯O12A	0.84	2.01	2.791 (2)	154
O11B—H11B⋯O12B	0.84	2.30	2.741 (2)	113
C24B—H24D⋯O12Aⁱ	0.99	2.52	3.475 (2)	162

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Symmetry code: (i) Inline graphic .

Acknowledgments

This study was financed by the State Funds for Scientific Research (grant DS/8220–4–0087–11).

supplementary crystallographic information

Comment

Apart from their interesting biological activities (Mitscher, 2005), quinolin-4(1H)-ones display dual fluorescence, the result of Excited State Intramolecular Proton Transfer (ESIPT), if they are substituted with –OH and phenyl in the pyridine-4(1H)-one ring in the vicinity of the carbonyl group and the N atom, respectively (Yushchenko et al., 2007). Influenced by the properties of the medium, ESIPT makes 3-hydroxy-2-phenylquinolin-4(1H)-ones interesting fluorescent probes sensitive to features of a medium (Bilokin' et al., 2009). Since ESIPT is believed to depend on the mutual orientation of the 1,4-dihydroquinoline and benzene fragments (Yushchenko et al., 2007), we undertook investigations into the structure of potential fluorescent sensors belonging to the latter group of compounds. Here the structure of 3-hydroxy-1-methyl-(-2-[4-(piperidin-1-yl)phenyl]quinolin-4(1H)-one is presented.

In the title compound (Fig. 1), the bond lengths and angles characterizing the geometry of the 2-phenylquinolin-4(1H)-one moiety are typical of this group of compounds (Czaun et al., 2002; Mphahlele et al., 2002; Mphahlele & El-Nahas, 2004). With respective average deviations from planarity of 0.0163 (1)° (A) or 0.0180 (1)° (B) and 0.0078 (1)° (A) or 0.0059 (1)° (B), the 1,4-dihydroquinoline and benzene ring systems are oriented at a dihedral angle of 69.9 (1)° (A) or 83.4 (1)° (B) (in crystalline 3-hydroxy-2-phenylquinolin-4(1H)-one: dimethyl sulfoxide, 1:1, this angle is equal to 45.2 (1)° (Czaun et al., 2002)). As mentioned above, the latter angle appears to be important for explaining the mechanism of ESIPT in this group of compounds (Yushchenko et al., 2007).

In the crystal lattice, two structurally similar but crystallographically independent molecules (A and B), linked via two O–H···O hydrogen bonds (Aakeröy et al., 1992), are present in the asymmetric unit (Table 1, Fig. 1). Molecules A are in contact with neighboring B ones through C–H···O (Novoa et al., 2006) interactions (Table 1, Fig. 2). Adjacent 1,4-dihydroquinoline units of molecules A are parallel – they lie at an angle of 0.0 (1)° – while molecules A and B are oriented at an angle of 32.8 (1)°. The O12–H12···O13 intramolecular hydrogen bonds (Table 1, Figs. 1 and 2) are the ones that may be involved in ESIPT; the phenomenon originally disclosed in 3-hydroxy-2-phenyl-4H-chromen-4-ones (Sengupta & Kasha, 1979), which are analogues of 3-hydroxy-2-phenylquinolin-4(1H)-ones.

Experimental

The title compound was synthesized in two steps. First a mixture of 2-(methylamino)benzoic acid, 2-bromo-1-(4-fluorophenyl)ethanone and potassium carbonate in dimethylformamide was heated at 325 K for 1 h to obtain 2-(4-fluorophenyl)-2-oxoethyl 2-(methylamino)benzoate. On further heating with polyphosphoric acid (395 K, 2 h), this yielded 2-(4-fluorophenyl)-3-hydroxy-1-methyl-quinolin-4(1H)-one (Hradil et al., 1999; Yushchenko et al., 2006). The latter compound was then separated, dissolved in piperidine and the solution stored in a sealed tube at 445 K for 50 h. The reactant mixture was subsequently poured into 1% aq HCl and the precipitate separated by filtration. Crystals suitable for X-ray investigations were grown from dimethylformamide (m.p. = 566–568 K).

The X-ray measurements were carried out at 180 K. Below this temperature, a phase transition occurs, which doubles parameter c of the unit cell.