2-(4-Fluoro­phen­yl)-3-hy­droxy-4H-chromen-4-one

Michał Wera; Ilia E Serdiuk; Alexander D Roshal; Jerzy Błażejowski

doi:10.1107/S1600536810045083

. 2010 Nov 10;66(Pt 12):o3122. doi: 10.1107/S1600536810045083

2-(4-Fluorophenyl)-3-hydroxy-4H-chromen-4-one

Michał Wera ^a, Ilia E Serdiuk ^b, Alexander D Roshal ^b, Jerzy Błażejowski ^a,^*

PMCID: PMC3011522 PMID: 21589426

Abstract

In the crystal structure of the title compound, C₁₅H₉FO₃, inversely oriented molecules form inversion dimers through pairs of O—H⋯O hydrogen bonds. The benzene ring is twisted at an angle of 12.0 (1)° relative to the 4H-chromene skeleton of the molecule. Adjacent 4H-chromene units are parallel in a given column or oriented at an angle of 50.0 (1)° in neighboring, inversely oriented, columns, forming a herringbone pattern.

Related literature

For general background to fluorescence in flavanol (3-hydroxy-2-phenyl-4H-chromen-4-one) and its derivatives, see: Demchenko et al. (2002 ▶); Pivovarenko et al. (2005 ▶); Roshal et al. (2003 ▶); Sengupta & Kasha (1979 ▶). For related structures, see: Cantrell & Stalzer (1982 ▶); Etter et al. (1986 ▶); Waller et al. (2003 ▶). For intermolecular interactions, see: Aakeröy et al. (1992 ▶); Dorn et al. (2005 ▶). For the synthesis, see: Smith et al. (1968 ▶).

Experimental

Crystal data

C₁₅H₉FO₃
M _r = 256.22
Monoclinic,
a = 15.5971 (9) Å
b = 3.8790 (2) Å
c = 19.1655 (12) Å
β = 103.906 (6)°
V = 1125.55 (11) Å³
Z = 4
Mo Kα radiation
μ = 0.12 mm⁻¹
T = 295 K
0.6 × 0.4 × 0.05 mm

Data collection

Oxford Diffraction Gemini R Ultra Ruby CCD diffractometer
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2008 ▶) T _min = 0.956, T _max = 0.991
7973 measured reflections
1999 independent reflections
1729 reflections with I > 2σ(I)
R _int = 0.026

Refinement

R[F ² > 2σ(F ²)] = 0.050
wR(F ²) = 0.113
S = 1.12
1999 reflections
176 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Data collection: CrysAlis CCD (Oxford Diffraction, 2008 ▶); cell refinement: CrysAlis RED (Oxford Diffraction, 2008 ▶); 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/S1600536810045083/xu5076sup1.cif

e-66-o3122-sup1.cif^{(17.7KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810045083/xu5076Isup2.hkl

e-66-o3122-Isup2.hkl^{(98.4KB, 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
O11—H11⋯O12	0.83 (3)	2.28 (3)	2.722 (2)	113 (3)
O11—H11⋯O12ⁱ	0.83 (3)	2.02 (3)	2.761 (2)	149 (3)

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Symmetry code: (i) Inline graphic .

Acknowledgments

This study was financed by the State Funds for Scientific Research (grant DS/8220–4-0087–0).

supplementary crystallographic information

Comment

3-Hydroxy-2-phenyl-4H-chromen-4-one (flavonol) and its derivatives exhibit dual fluorescence in liquid phases originating from the Excited State Intramolecular Proton Transfer (ESIPT) phenomenon (Sengupta & Kasha, 1979). Since the fluorescence of flavonols depends strongly on the properties of the medium, the compounds can be applied as analytical probes in chemistry, biochemistry, biology and medicine (Demchenko et al., 2002). Continuing our investigations into this group of compounds (Roshal et al., 2003; Pivovarenko et al., 2005) we now present the crystal structure of a flavonol derivative – 2-(4-fluorophenyl)-3-hydroxy-4H-chromen-4-one.

In the title compound (Fig. 1), the bond lengths and angles characterizing the geometry of the 2-phenyl-4H-chromen-4-one (flavone) moiety are typical of this group of compounds (Cantrell & Stalzer, 1982; Etter et al., 1986; Waller et al., 2003). With respective average deviations from planarity of 0.0147 (2)° and 0.0020 (2)°, the 4H-chromene and benzene ring systems are oriented at a dihedral angle of 12.0 (1)° (in the case of flavonol this angle is equal to 5.5 (1)° (Etter et al., 1986)).

In the crystal structure, the inversely oriented molecules form dimers through a pair of intermolecular O—H···O (Aakeröy et al., 1992) bonds (Table 1, Fig. 2). Dimers oriented in parallel – linked by C—F···π (Dorn et al., 2005) contacts (Table 2, Fig. 2) – are arranged in columns along the b axis which are dispersively stabilized in the crystal lattice. The adjacent 4H-chromene moieties are parallel in a given column or oriented at an angle of 50.0 (1) in the two neighboring, inversely oriented, columns, which forms a herringbone pattern. The O11—H11···O12 intramolecular hydrogen bond (Table 1, Figs. 1 and 2) is the one involved in the ESIPT phenomenon, characteristic of flavonols (Sengupta & Kasha, 1979).

Experimental

The title compound was synthesized following the procedure described by Smith et al., 1968. Briefly, 3-(4-fluorophenyl)-1-(2-hydroxyphenyl)prop-2-en-1-one was synthesized first by the condensation of 1-(2-hydroxyphenyl)ethanone with 4-fluorobenzaldehyde in methanol/50% aqueous NaOH (1/1 v/v), precipitated by neutralizing the reaction mixture with aqueous HCl and separated by filtration. The product thus obtained was subjected to oxidative cyclization in alkaline methanol/H₂O₂ to yield 2-(4-fluorophenyl)-3-hydroxy-4H-chromen-4-one. The filtered product was purified chromatographically (Silica Gel, chloroform/methanol, 20/1 v/v) and yellow crystals suitable for X-ray investigations were grown from absolute ethanol (m.p. = 442–443 K).