3-Hy­droxy-2-(4-hy­droxy­phen­yl)-4H-chromen-4-one

Michał Wera; Vasyl G Pivovarenko; Jerzy Błażejowski

doi:10.1107/S1600536810053407

. 2011 Jan 8;67(Pt 2):o264–o265. doi: 10.1107/S1600536810053407

3-Hydroxy-2-(4-hydroxyphenyl)-4H-chromen-4-one

Michał Wera ^a, Vasyl G Pivovarenko ^b, Jerzy Błażejowski ^a,^*

PMCID: PMC3051623 PMID: 21522957

Abstract

In the title compound, C₁₅H₁₀O₄, the benzene ring is twisted at an angle of 20.7 (1)° relative to the 4H-chromene skeleton. In the crystal, adjacent molecules are linked via a network of O—H⋯O and C—H⋯O hydrogen bonds. The mean planes of adjacent 4H-chromene moieties are parallel or oriented at an angle of 20.9 (1)° in the crystal structure.

Related literature

For general background to the properties of flavones (derivatives of 2-phenyl-4H-chromen-4-one) and fluorescence of flavonols (derivatives of 3-hydroxy-2-phenyl-4H-chromen-4-one), see: Bader et al. (2003 ▶); Choulier et al. (2010 ▶); Demchenko (2009 ▶); Klymchenko & Demchenko (2003 ▶); Nijveldt et al. (2001 ▶); Pivovarenko et al. (2004 ▶); Roshal et al. (2003 ▶); Sengupta & Kasha (1979 ▶). For related structures, see: Etter et al. (1986 ▶); Kumar et al. (1998 ▶); Waller et al. (2003 ▶). For intermolecular interactions, see: Aakeröy et al. (1992 ▶); Novoa et al. (2006 ▶). For the synthesis, see: Bader et al. (2003 ▶); Sobottka et al. (2000 ▶).

Experimental

Crystal data

C₁₅H₁₀O₄
M _r = 254.23
Monoclinic,
a = 3.7897 (3) Å
b = 17.6380 (15) Å
c = 16.7745 (16) Å
β = 90.968 (9)°
V = 1121.09 (17) Å³
Z = 4
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 295 K
0.6 × 0.2 × 0.2 mm

Data collection

Oxford Diffraction Gemini R Ultra Ruby CCD diffractometer
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2008 ▶) T _min = 0.329, T _max = 1.000
9273 measured reflections
1979 independent reflections
920 reflections with I > 2σ(I)
R _int = 0.075

Refinement

R[F ² > 2σ(F ²)] = 0.060
wR(F ²) = 0.155
S = 0.84
1979 reflections
179 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.28 e Å⁻³
Δρ_min = −0.31 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/S1600536810053407/xu5114sup1.cif

e-67-0o264-sup1.cif^{(17.6KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810053407/xu5114Isup2.hkl

e-67-0o264-Isup2.hkl^{(97.4KB, 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⋯O19ⁱ	0.83 (5)	2.10 (5)	2.832 (4)	148 (4)
O19—H19⋯O12ⁱⁱ	0.91 (5)	1.79 (5)	2.705 (4)	176 (5)
C7—H7⋯O11ⁱⁱⁱ	0.93	2.47	3.267 (4)	144

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

Acknowledgments

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

supplementary crystallographic information

Comment

Flavones (derivatives of 2-phenyl-4H-chromen-4-one) appear in numerous natural systems and have been comprehensively investigated in view of their antioxidant features (Nijveldt et al., 2001). Related to flavones, 3-hydroxy-2-phenyl-4H-chromen-4-one (flavonols) exhibit dual fluorescence in the condensed phases resulting from the Excited State Intramolecular Proton Transfer (ESIPT) (Sengupta & Kasha, 1979). In flavonols this phenomenon is strongly affected by molecules from their environment, which makes the compounds interesting fluorescent sensors for analytical applications in chemistry, biology, biochemistry, ecology and medicine (Klymchenko & Demchenko, 2003; Demchenko, 2009; Choulier et al., 2010). Continuing our investigations into the physical chemistry of flavonols (Bader et al., 2003; Roshal et al., 2003; Pivovarenko et al., 2004), we present the crystal structure of 3-hydroxy-2-(4-hydroxyphenyl)-4H-chromen-4-one in the hope that its structural and fluorescent features will appear interesting and helpful in its practical applications.

In the title compound (Fig. 1), the bond lengths and angles characterizing the geometry of the 2-phenyl-4H-chromen-4-one moiety are typical of this group of compounds (Etter et al., 1986; Kumar et al., 1998; Waller et al., 2003). With respective average deviations from planarity of 0.0187 (1)° and 0.0041 (1)°, the 4H-chromene and benzene ring systems are oriented at a dihedral angle of 20.7 (1)° (in the case of flavonol this angle is 5.5 (1)° (Etter et al., 1986)). The mean planes of the adjacent 4H-chromen-4-one moieties are either parallel (remain at an angle of 0.0 (1)°) or inclined at 20.9 (1)°.

The crystal structure of the title compound is stabilized by a network of O—H···O (Aakeröy et al., 1992) (Table 1, Fig. 2) and C—H···O (Novoa et al., 2006) (Table 1, Fig. 2) hydrogen bonds, and by non-specific dispersive interactions. Each of the two OH groups is involved in hydrogen bonds as H atom acceptor and donor. 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 in two steps. First, 3-hydroxy-2-(4-methoxyphenyl)-4H-chromen-4-one was prepared by alkaline condensation of 4-methoxybenzaldehyde with 1-(2-hydroxyphenyl)ethanone and subsequent oxidative heterocyclization of the product with hydrogen peroxide (the light green-yellow precipitate of the product was recrystallized twice from a 1% solution of acetic acid in ethanol) (Bader et al., 2003). Next, the 3-hydroxy-2-(4-methoxyphenyl)-4H-chromen-4-one thus obtained was converted to 3-hydroxy-2-(4-hydroxyphenyl)-4H-chromen-4-one by maintaining a solution of the former compound in molten pyridinium chloride at 495 K for 20 minutes, then cooling the reactant mixture, and pouring it into 1% aqueous HCl. Pale brown crystals suitable for X-ray investigations were grown from DMF solutions of the filtered precipitate of the final product (m.p. = 557–558 K; lit. 555–558 K (Sobottka et al., 2000)).