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Acta Cryst. (2013). E69, o895    [ doi:10.1107/S1600536813010982 ]

2-(4-Hydroxyphenyl)-3-methoxy-4H-chromen-4-one

I. E. Serdiuk, M. Wera, A. D. Roshal and J. Blazejowski

Abstract top

In the title compound, C16H12O4, the substituent benzene ring and methoxy group are twisted relative to the 4H-chromene skeleton by 24.1 (1) and 61.3 (1)°, respectively. In the crystal, molecules are connected by classical O-H...O and weak C-H...O hydrogen bonds, forming chains parallel to [201]. The 4H-chromene ring systems of adjacent molecules are either parallel or inclined at an angle of 28.9 (1)°.

Comment top

Flavones (derivatives of 2-phenyl-4H-chromen-4-one) occur in numerous natural systems and have been thoroughly investigated because of their biological relevance (Ma et al., 2012). Related to flavones, 3-hydroxy-2-phenyl-4H-chromen-4-ones (flavonols) exhibit dual fluorescence in condensed phases due to Excited State Intramolecular Proton Transfer (ESIPT) which makes the compounds interesting fluorescent sensors for analytical applications (Demchenko, 2009). Here we present the crystal structure of the flavonol derivative – 2-(4-hydroxyphenyl)-3-methoxy-4H-chromen-4-one – in which ESIPT does not occur. This makes the compound a convenient reference substance in investigations of emission phenomena in this group of compounds.

In the title compound (Fig.1), the bond lengths and angles characterizing the geometry of the 4H-chromen-4-one moiety are similar to those of other compounds of this group (Wera et al., 2011a,b). With respective average deviations from planarity of 0.0309 (1) Å and 0.0037 (1) Å, the 4H-chromen-4-one and benzene ring systems are oriented at a dihedral angle of 24.1 (1)° [in the case of 3-hydroxy-2-(4-hydroxyphenyl)-4H-chromen-4-one this angle is 20.7 (1)° (Wera et al., 2011a), and in 3-hydroxy-2-(4-methoxyphenyl)-4H-chromen-4-one it is 12.3 (1)° (Wera et al., 2011b)]. The methoxy group is twisted relative to the 4H-chromen-4-one ring system through an angle of 61.3 (1)°.

In the crystal structure, molecules connected by a network of O–H···O (Aakeröy et al., 1992), the C(10) motif (Etter et al., 1990) and C–H···O (Novoa et al., 2006) interactions (Table 1, Figs. 2 and 3), are arranged in layers (Fig. 2) that are dispersively stabilized in the crystal lattice (Fig. 3). The 4H-chromene cores are either parallel or oriented at an angle of 28.9 (1)°, while the benzene rings are parallel or inclined at an angle of 76.6 (1)°.

Related literature top

For general features of flavones and flavonols (derivatives of 3-hydroxy-2-phenyl-4H-chromen-4-one), see: Demchenko (2009); Ma et al. (2012). For related structures, see: Wera et al. (2011a,b). For intermolecular interactions, see: Aakeröy et al. (1992); Etter et al. (1990); Novoa et al. (2006). For the synthesis, see: Bader et al. (2003); Wera et al. (2011b).

Experimental top

The title compound was synthesized in four steps. First, 1-(2-hydroxyphenyl)-3-{4-[(4-methoxybenzyl)oxy]phenyl}prop-2-en-1-one (chalcone) was prepared by the condensation (with the elimination of water) of 1-(2-hydroxyphenyl)ethanone with 4-[(4-methoxybenzyl)oxy]benzaldehyde in N-methylpyrrolidone/aqueous KOH (1/1 v/v), then precipitated by neutralizing the reaction mixture with aqueous HCl and recrystallized from methanol. Next, chalcone was oxidatively cyclized in a K2CO3/methanol/H2O2 mixture, yielding to 3-hydroxy-2-{4-[(4-methoxybenzyl)oxy]phenyl}-4H-chromen-4-one (Bader et al., 2003; Wera et al., 2011b). This product was then alkylated by dimethyl sulfate in an acetonitrile/K2CO3 mixture. Finally, the 3-methoxy-2-{4-[(4-methoxybenzyl)oxy]phenyl}-4H-chromen-4-one thus obtained was heated in acetic acid to give the title compound [2-(4-hydroxyphenyl)-3-methoxy-4H-chromen-4-one] with a yield of 34%. Pale yellow crystals suitable for X-ray investigations were grown from 1,4-dioxane solutions of the chromatographically purified (Silica Gel, 2-propanol/chloroform, 1/20 v/v) precipitate of the final product (m.p. = 506–507 K).

Refinement top

H atoms of C–H bonds were positioned geometrically, with C–H = 0.93 Å and 0.96 Å for the aromatic and methyl H atoms, respectively, and constrained to ride on their parent atoms with Uiso(H) = xUeq(C) where x = 1.2 for the aromatic H and 1.5 for methyl H atoms. Hydroxy H atom was located on a difference Fourier map and refined isotropically with Uiso(H) = 1.5Ueq(O).

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2008); cell refinement: CrysAlis CCD (Oxford Diffraction, 2008); data reduction: CrysAlis RED (Oxford Diffraction, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound showing the atom labeling scheme. Displacement ellipsoids are drawn at the 25% probability level, and H atoms are shown as small spheres of arbitrary radius.
[Figure 2] Fig. 2. Molecular arrangement in the crystal structure. The O–H···O and C–H···O interactions are represented by dashed lines. H atoms not involved in interactions have been omitted. [Symmetry codes: (i) x + 1, –y – 1/2, z + 1/2; (ii) x – 1, –y + 1/2, z – 1/2.]
[Figure 3] Fig. 3. Layers in the crystal structure. The O–H···O and C–H···O interactions are represented by dashed lines. H atoms not involved in interactions have been omitted.
2-(4-Hydroxyphenyl)-3-methoxy-4H-chromen-4-one top
Crystal data top
C16H12O4F(000) = 560
Mr = 268.26Dx = 1.416 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.7107 Å
Hall symbol: -P 2ybcCell parameters from 2245 reflections
a = 8.7191 (5) Åθ = 3.3–25.1°
b = 8.8978 (4) ŵ = 0.10 mm1
c = 16.706 (1) ÅT = 295 K
β = 103.801 (6)°Prism, pale yellow
V = 1258.65 (12) Å30.6 × 0.45 × 0.25 mm
Z = 4
Data collection top
Oxford Diffraction Gemini R Ultra Ruby CCD
diffractometer
2245 independent reflections
Radiation source: Enhance (Mo) X-ray Source1801 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.021
Detector resolution: 10.4002 pixels mm-1θmax = 25.1°, θmin = 3.3°
ω scansh = 710
Absorption correction: multi-scan
(CrysAlis RED; Oxford Diffraction, 2008)
k = 1010
Tmin = 0.943, Tmax = 0.970l = 1819
5100 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.040Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.107H atoms treated by a mixture of independent and constrained refinement
S = 1.03 w = 1/[σ2(Fo2) + (0.0515P)2 + 0.1866P]
where P = (Fo2 + 2Fc2)/3
2245 reflections(Δ/σ)max < 0.001
185 parametersΔρmax = 0.14 e Å3
0 restraintsΔρmin = 0.18 e Å3
Crystal data top
C16H12O4V = 1258.65 (12) Å3
Mr = 268.26Z = 4
Monoclinic, P21/cMo Kα radiation
a = 8.7191 (5) ŵ = 0.10 mm1
b = 8.8978 (4) ÅT = 295 K
c = 16.706 (1) Å0.6 × 0.45 × 0.25 mm
β = 103.801 (6)°
Data collection top
Oxford Diffraction Gemini R Ultra Ruby CCD
diffractometer
2245 independent reflections
Absorption correction: multi-scan
(CrysAlis RED; Oxford Diffraction, 2008)
1801 reflections with I > 2σ(I)
Tmin = 0.943, Tmax = 0.970Rint = 0.021
5100 measured reflectionsθmax = 25.1°
Refinement top
R[F2 > 2σ(F2)] = 0.040H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.107Δρmax = 0.14 e Å3
S = 1.03Δρmin = 0.18 e Å3
2245 reflectionsAbsolute structure: ?
185 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O10.26225 (13)0.08174 (12)0.03249 (6)0.0445 (3)
C20.31549 (18)0.06240 (17)0.03302 (10)0.0390 (4)
C30.2506 (2)0.15818 (18)0.02953 (10)0.0443 (4)
C40.1209 (2)0.1136 (2)0.09642 (10)0.0503 (5)
C50.0405 (2)0.1077 (3)0.16006 (12)0.0656 (6)
H50.09150.04910.20460.079*
C60.0777 (3)0.2560 (3)0.15735 (13)0.0762 (7)
H60.15400.29790.20010.091*
C70.0028 (3)0.3448 (3)0.09160 (13)0.0729 (6)
H70.02950.44590.09060.087*
C80.1101 (2)0.2854 (2)0.02795 (11)0.0589 (5)
H80.16070.34490.01630.071*
C90.07400 (19)0.0433 (2)0.09613 (10)0.0488 (5)
C100.14684 (19)0.1346 (2)0.03126 (10)0.0451 (4)
O110.29961 (17)0.30466 (13)0.02436 (8)0.0603 (4)
O120.05411 (16)0.20337 (16)0.15021 (8)0.0712 (4)
C130.43909 (17)0.09082 (16)0.10765 (9)0.0358 (4)
C140.4500 (2)0.00252 (18)0.17590 (10)0.0460 (4)
H140.37720.07990.17330.055*
C150.5654 (2)0.01740 (19)0.24656 (10)0.0483 (4)
H150.56940.04560.29140.058*
C160.67592 (19)0.12985 (17)0.25180 (10)0.0403 (4)
C170.66761 (19)0.22373 (17)0.18547 (10)0.0417 (4)
H170.74140.30030.18850.050*
C180.55044 (19)0.20481 (16)0.11453 (10)0.0406 (4)
H180.54580.26970.07040.049*
C190.3675 (3)0.3531 (2)0.09013 (14)0.0818 (7)
H19A0.28690.35710.14050.123*
H19B0.41300.45110.07780.123*
H19C0.44810.28350.09620.123*
O200.78716 (16)0.14223 (15)0.32342 (8)0.0600 (4)
H200.867 (3)0.209 (3)0.3198 (15)0.090*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0465 (7)0.0475 (7)0.0342 (6)0.0080 (5)0.0007 (5)0.0006 (5)
C20.0394 (9)0.0405 (9)0.0364 (9)0.0031 (7)0.0078 (7)0.0004 (7)
C30.0477 (10)0.0457 (9)0.0382 (10)0.0106 (8)0.0074 (8)0.0029 (7)
C40.0425 (10)0.0709 (12)0.0363 (10)0.0205 (9)0.0075 (8)0.0040 (8)
C50.0418 (10)0.1093 (18)0.0412 (11)0.0004 (11)0.0011 (9)0.0086 (11)
C60.0557 (13)0.123 (2)0.0467 (13)0.0313 (13)0.0047 (10)0.0234 (13)
C70.0751 (14)0.0945 (16)0.0489 (13)0.0405 (13)0.0144 (11)0.0157 (11)
C80.0638 (12)0.0716 (13)0.0405 (11)0.0243 (10)0.0109 (9)0.0053 (9)
C90.0357 (9)0.0756 (12)0.0339 (9)0.0045 (8)0.0062 (7)0.0050 (8)
C100.0365 (9)0.0655 (11)0.0325 (9)0.0077 (8)0.0069 (7)0.0073 (8)
O110.0815 (10)0.0453 (7)0.0497 (8)0.0114 (6)0.0069 (7)0.0083 (6)
O120.0654 (9)0.0919 (10)0.0484 (8)0.0313 (8)0.0021 (7)0.0173 (7)
C130.0363 (8)0.0346 (8)0.0356 (9)0.0031 (7)0.0068 (7)0.0008 (6)
C140.0451 (9)0.0458 (9)0.0427 (10)0.0103 (8)0.0018 (8)0.0065 (7)
C150.0497 (10)0.0511 (10)0.0389 (10)0.0079 (8)0.0001 (8)0.0113 (8)
C160.0391 (9)0.0412 (8)0.0371 (9)0.0008 (7)0.0020 (7)0.0038 (7)
C170.0413 (9)0.0362 (8)0.0471 (10)0.0060 (7)0.0092 (8)0.0029 (7)
C180.0458 (10)0.0370 (8)0.0387 (9)0.0021 (7)0.0097 (8)0.0056 (7)
C190.1109 (19)0.0646 (13)0.0691 (15)0.0072 (13)0.0199 (14)0.0224 (11)
O200.0549 (8)0.0682 (9)0.0459 (8)0.0154 (6)0.0100 (6)0.0035 (6)
Geometric parameters (Å, º) top
O1—C101.3627 (18)C9—C101.382 (2)
O1—C21.3633 (19)O11—C191.433 (3)
C2—C31.362 (2)C13—C181.390 (2)
C2—C131.462 (2)C13—C141.395 (2)
C3—O111.368 (2)C14—C151.368 (2)
C3—C41.443 (2)C14—H140.9300
C4—O121.239 (2)C15—C161.377 (2)
C4—C91.455 (3)C15—H150.9300
C5—C61.362 (3)C16—O201.3530 (19)
C5—C91.399 (2)C16—C171.376 (2)
C5—H50.9300C17—C181.378 (2)
C6—C71.384 (3)C17—H170.9300
C6—H60.9300C18—H180.9300
C7—C81.371 (3)C19—H19A0.9600
C7—H70.9300C19—H19B0.9600
C8—C101.383 (3)C19—H19C0.9600
C8—H80.9300O20—H200.93 (3)
C10—O1—C2121.13 (13)C9—C10—C8122.28 (16)
C3—C2—O1120.33 (14)C3—O11—C19114.71 (15)
C3—C2—C13129.24 (15)C18—C13—C14117.18 (14)
O1—C2—C13110.41 (12)C18—C13—C2123.70 (14)
C2—C3—O11118.76 (15)C14—C13—C2119.10 (14)
C2—C3—C4121.84 (16)C15—C14—C13121.37 (15)
O11—C3—C4119.09 (14)C15—C14—H14119.3
O12—C4—C3122.05 (18)C13—C14—H14119.3
O12—C4—C9122.48 (17)C14—C15—C16120.58 (15)
C3—C4—C9115.47 (15)C14—C15—H15119.7
C6—C5—C9120.2 (2)C16—C15—H15119.7
C6—C5—H5119.9O20—C16—C17123.49 (15)
C9—C5—H5119.9O20—C16—C15117.29 (15)
C5—C6—C7120.58 (19)C17—C16—C15119.22 (15)
C5—C6—H6119.7C16—C17—C18120.29 (14)
C7—C6—H6119.7C16—C17—H17119.9
C8—C7—C6120.7 (2)C18—C17—H17119.9
C8—C7—H7119.6C17—C18—C13121.35 (14)
C6—C7—H7119.6C17—C18—H18119.3
C7—C8—C10118.22 (19)C13—C18—H18119.3
C7—C8—H8120.9O11—C19—H19A109.5
C10—C8—H8120.9O11—C19—H19B109.5
C10—C9—C5117.95 (18)H19A—C19—H19B109.5
C10—C9—C4119.33 (15)O11—C19—H19C109.5
C5—C9—C4122.71 (17)H19A—C19—H19C109.5
O1—C10—C9121.69 (16)H19B—C19—H19C109.5
O1—C10—C8116.01 (15)C16—O20—H20112.6 (15)
C10—O1—C2—C31.9 (2)C4—C9—C10—O10.3 (2)
C10—O1—C2—C13179.79 (13)C5—C9—C10—C80.0 (3)
O1—C2—C3—O11175.76 (14)C4—C9—C10—C8178.69 (17)
C13—C2—C3—O112.2 (3)C7—C8—C10—O1178.60 (17)
O1—C2—C3—C42.3 (2)C7—C8—C10—C90.1 (3)
C13—C2—C3—C4175.66 (15)C2—C3—O11—C19120.39 (19)
C2—C3—C4—O12174.71 (16)C4—C3—O11—C1965.9 (2)
O11—C3—C4—O121.2 (3)C3—C2—C13—C1823.8 (3)
C2—C3—C4—C95.1 (2)O1—C2—C13—C18158.16 (14)
O11—C3—C4—C9178.60 (15)C3—C2—C13—C14157.69 (17)
C9—C5—C6—C70.1 (3)O1—C2—C13—C1420.4 (2)
C5—C6—C7—C80.0 (3)C18—C13—C14—C150.0 (2)
C6—C7—C8—C100.1 (3)C2—C13—C14—C15178.62 (15)
C6—C5—C9—C100.1 (3)C13—C14—C15—C160.8 (3)
C6—C5—C9—C4178.73 (19)C14—C15—C16—O20179.61 (16)
O12—C4—C9—C10175.76 (16)C14—C15—C16—C170.9 (3)
C3—C4—C9—C104.1 (2)O20—C16—C17—C18179.71 (15)
O12—C4—C9—C55.6 (3)C15—C16—C17—C180.3 (2)
C3—C4—C9—C5174.56 (16)C16—C17—C18—C130.5 (2)
C2—O1—C10—C92.9 (2)C14—C13—C18—C170.7 (2)
C2—O1—C10—C8175.60 (15)C2—C13—C18—C17177.91 (14)
C5—C9—C10—O1178.42 (15)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O20—H20···O12i0.93 (3)1.77 (3)2.648 (2)157 (2)
C7—H7···O20ii0.932.563.337 (3)141
Symmetry codes: (i) x+1, y1/2, z+1/2; (ii) x1, y+1/2, z1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O20—H20···O12i0.93 (3)1.77 (3)2.648 (2)157 (2)
C7—H7···O20ii0.932.563.337 (3)141
Symmetry codes: (i) x+1, y1/2, z+1/2; (ii) x1, y+1/2, z1/2.
Acknowledgements top

This study was financed by the State Funds for Scientific Research (grant DS/530–8220–D184–3).

references
References top

Aakeröy, C. B., Seddon, K. R. & Leslie, M. (1992). Struct. Chem. 3, 63–65.

Bader, A. N., Pivovarenko, V., Demchenko, A. P., Ariese, F. & Gooijer, C. (2003). Spectrochim. Acta Part A, 59, 1593–1603.

Demchenko, A. P. (2009). In Introduction to Fluorescence Sensing. The Netherlands: Springer Science and Business Media BV.

Etter, M. C., MacDonald, J. C. & Bernstein, J. (1990). Acta Cryst. B46, 256–262.

Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854.

Ma, J., Liu, Y., Chen, L., Xie, Y., Wang, L.-Y. & Xie, M.-X. (2012). Food Chem. 132, 663–670.

Novoa, J. J., Mota, F. & D'Oria, E. (2006). Hydrogen BondingNew Insights, edited by S. Grabowski, pp. 193–244. The Netherlands: Springer.

Oxford Diffraction (2008). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Spek, A. L. (2009). Acta Cryst. D65, 148–155.

Wera, M., Pivovarenko, V. G. & Błażejowski, J. (2011a). Acta Cryst. E67, o264–o265.

Wera, M., Serdiuk, I. E., Roshal, A. D. & Błażejowski, J. (2011b). Acta Cryst. E67, o440.