organic compounds
3-(4-Methylphenyl)-4H-chromen-4-one
aDepartment of Applied Chemistry, Dongduk Women's University, Seoul 136-714, Republic of Korea
*Correspondence e-mail: dskoh@dongduk.ac.kr
In the title compound, C16H12O2, the dihedral angle formed between the plane of the chromenone ring system (r.m.s. deviation = 0.031 Å) and the pendant benzene ring is 31.09 (5)°. In the crystal, weak C—H⋯O hydrogen bonds link the molecules into C(6) chains propagating along the a-axis direction.
Keywords: crystal structure; chromene; isoflavones.
CCDC reference: 2088523
Structure description
Isoflavones are flavonoid polyphenols with a general C6—C3—C6 carbon-atom skeleton. Since isoflavones have a substituent at the 2-position of the flavonoid skeleton, they exhibit structural differences from other compounds belonging to et al., 2000). Recent research has shown that isoflavones have broad biological activities with resspect to osteoporosis (Ye et al., 2006), anticancer activity (Messina et al., 2009), cardiovascular diseases (Zhan et al., 2005) and the inhibition of thyroid peroxidase (Chang et al., 2000). As part of our ongoing studies of isoflavones (Ahn et al., 2020; Shin et al., 2020), the title compound was synthesized and its was determined.
having a substituent at the 3-position. Isoflavones are sometimes classified as phytoestrogens, and they also exhibit different physiological functions from other (TikkanenThe molecular structure of the title compound, C16H12O2, is shown in Fig. 1. The chromenone ring system (C1–C9/O2) is slightly twisted from planarity, with a maximum deviation of 0.059 Å at C2 (root–mean–square deviation = 0.031 Å). The dihedral angle formed between the mean plane of the chromenone ring system and the pendant benzene (C10–C15) ring is 31.09 (5)°. In the crystal, weak C—H⋯O hydrogen bonds link the molecules into C(6) chains propagating along the a-axis direction (Table 1, Fig. 2).
Synthesis and crystallization
The title compound was synthesized in three steps from the commercially available starting materials 2-hydoxyacetophenone and 4-methylbenzaldehyde according to the reaction scheme shown in Fig. 3. To a solution of 2-hydoxyacetophenone (408 mg, 3 mmol) in 40 ml of ethanol was added 4-methylbenzaldehyde (360 mg, 3 mmol) and the temperature was adjusted to around 277 K in an ice-bath. To the cooled reaction mixture were added 4 ml of 30% aqueous KOH solution and the reaction mixture was stirred at room temperature for 3 h. This mixture was poured into iced water (100 ml) and was acidified (pH = 2) with 2 M HCl solution to give a precipitate. Filtration and washing with water afforded crude solid of chalcone compound (I). To a solution of I (1.5 mmol, 357 mg) in 20 ml aqueous ethanol (H2O:ethanol = 1:2) was added excess sodium acetate and the solution was refluxed at 362 K for 2 h. The reaction mixture was cooled to room temperature and was poured into iced water (50 ml) to give a precipitate of the flavanone compound II. Compound II (163 mg, 0.5 mmol) was dissolved in 15 ml of methanol and the temperature was adjusted to around 327 K. To the clear solution were added catalytic amount of p-toluene sulfonic acid and 1.2eq of thallium(III) nitrate trihydrate and the mixture was refluxed for 5 h. The reaction mixture was cooled to room temperature and the resulting precipitate was filtered and washed with water. This solid was recrystallized from an ethanol solution to obtain single crystals of the title compound.
Refinement
Crystal data, data collection and structure .
details are summarized in Table 2Structural data
CCDC reference: 2088523
https://doi.org/10.1107/S2414314621005903/hb4386sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314621005903/hb4386Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S2414314621005903/hb4386Isup3.cml
Data collection: APEX2 (Bruker, 2012); cell
SAINT (Bruker, 2012); data reduction: SAINT (Bruker, 2012); program(s) used to solve structure: SHELXS (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014/7 (Sheldrick, 2015); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and publCIF (Westrip, 2010).C16H12O2 | Z = 2 |
Mr = 236.26 | F(000) = 248 |
Triclinic, P1 | Dx = 1.339 Mg m−3 |
a = 6.4514 (3) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 7.0785 (4) Å | Cell parameters from 7663 reflections |
c = 13.3144 (7) Å | θ = 3.0–28.3° |
α = 78.906 (2)° | µ = 0.09 mm−1 |
β = 85.276 (2)° | T = 223 K |
γ = 79.628 (2)° | Block, colourless |
V = 586.19 (5) Å3 | 0.56 × 0.31 × 0.12 mm |
Bruker PHOTON II M14 CCD diffractometer | 2459 reflections with I > 2σ(I) |
φ and ω scans | Rint = 0.032 |
Absorption correction: multi-scan (SADABS; Bruker, 2012) | θmax = 28.3°, θmin = 3.0° |
Tmin = 0.666, Tmax = 0.746 | h = −8→8 |
18172 measured reflections | k = −9→9 |
2904 independent reflections | l = −17→17 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.044 | H-atom parameters constrained |
wR(F2) = 0.124 | w = 1/[σ2(Fo2) + (0.0506P)2 + 0.2032P] where P = (Fo2 + 2Fc2)/3 |
S = 1.06 | (Δ/σ)max < 0.001 |
2904 reflections | Δρmax = 0.27 e Å−3 |
164 parameters | Δρmin = −0.22 e Å−3 |
0 restraints |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.56922 (19) | 0.72771 (17) | 0.62667 (10) | 0.0304 (3) | |
O1 | 0.72856 (15) | 0.67806 (17) | 0.67655 (8) | 0.0452 (3) | |
C2 | 0.35627 (19) | 0.78209 (17) | 0.67070 (9) | 0.0290 (3) | |
C3 | 0.19573 (19) | 0.84130 (19) | 0.60689 (9) | 0.0318 (3) | |
H3 | 0.0619 | 0.8826 | 0.6365 | 0.038* | |
O2 | 0.20859 (13) | 0.84701 (14) | 0.50433 (7) | 0.0338 (2) | |
C4 | 0.40159 (19) | 0.78707 (17) | 0.45916 (9) | 0.0294 (3) | |
C5 | 0.4074 (2) | 0.7839 (2) | 0.35475 (10) | 0.0365 (3) | |
H5 | 0.2836 | 0.8215 | 0.3182 | 0.044* | |
C6 | 0.5979 (2) | 0.7246 (2) | 0.30617 (11) | 0.0408 (3) | |
H6 | 0.6040 | 0.7197 | 0.2359 | 0.049* | |
C7 | 0.7824 (2) | 0.6717 (2) | 0.36019 (11) | 0.0416 (3) | |
H7 | 0.9121 | 0.6326 | 0.3263 | 0.050* | |
C8 | 0.7736 (2) | 0.67708 (19) | 0.46305 (11) | 0.0361 (3) | |
H8 | 0.8984 | 0.6430 | 0.4989 | 0.043* | |
C9 | 0.58123 (19) | 0.73260 (16) | 0.51535 (9) | 0.0289 (3) | |
C10 | 0.3097 (2) | 0.77022 (18) | 0.78255 (9) | 0.0319 (3) | |
C11 | 0.4540 (2) | 0.8019 (2) | 0.84770 (11) | 0.0408 (3) | |
H11 | 0.5867 | 0.8302 | 0.8209 | 0.049* | |
C12 | 0.4033 (3) | 0.7920 (2) | 0.95158 (11) | 0.0467 (4) | |
H12 | 0.5035 | 0.8125 | 0.9940 | 0.056* | |
C13 | 0.2093 (3) | 0.7528 (2) | 0.99470 (11) | 0.0450 (3) | |
C14 | 0.0661 (2) | 0.7211 (2) | 0.93000 (11) | 0.0469 (4) | |
H14 | −0.0672 | 0.6952 | 0.9570 | 0.056* | |
C15 | 0.1159 (2) | 0.7269 (2) | 0.82625 (10) | 0.0400 (3) | |
H15 | 0.0173 | 0.7012 | 0.7846 | 0.048* | |
C16 | 0.1555 (3) | 0.7426 (3) | 1.10810 (12) | 0.0646 (5) | |
H16A | 0.2235 | 0.6185 | 1.1454 | 0.097* | |
H16B | 0.0038 | 0.7546 | 1.1206 | 0.097* | |
H16C | 0.2046 | 0.8482 | 1.1310 | 0.097* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0281 (6) | 0.0288 (6) | 0.0353 (6) | −0.0060 (4) | −0.0082 (5) | −0.0047 (5) |
O1 | 0.0290 (5) | 0.0644 (7) | 0.0421 (5) | −0.0023 (4) | −0.0131 (4) | −0.0094 (5) |
C2 | 0.0293 (6) | 0.0282 (6) | 0.0307 (6) | −0.0069 (4) | −0.0057 (4) | −0.0047 (4) |
C3 | 0.0274 (6) | 0.0379 (6) | 0.0298 (6) | −0.0038 (5) | −0.0036 (4) | −0.0062 (5) |
O2 | 0.0263 (4) | 0.0444 (5) | 0.0301 (4) | −0.0018 (4) | −0.0074 (3) | −0.0066 (4) |
C4 | 0.0288 (6) | 0.0273 (6) | 0.0328 (6) | −0.0054 (4) | −0.0038 (5) | −0.0058 (4) |
C5 | 0.0398 (7) | 0.0375 (7) | 0.0338 (6) | −0.0075 (5) | −0.0081 (5) | −0.0068 (5) |
C6 | 0.0504 (8) | 0.0404 (7) | 0.0335 (6) | −0.0100 (6) | 0.0016 (6) | −0.0106 (5) |
C7 | 0.0389 (7) | 0.0401 (7) | 0.0460 (8) | −0.0056 (6) | 0.0061 (6) | −0.0133 (6) |
C8 | 0.0296 (6) | 0.0344 (6) | 0.0446 (7) | −0.0040 (5) | −0.0030 (5) | −0.0085 (5) |
C9 | 0.0290 (6) | 0.0249 (5) | 0.0337 (6) | −0.0060 (4) | −0.0046 (5) | −0.0048 (4) |
C10 | 0.0344 (6) | 0.0315 (6) | 0.0304 (6) | −0.0056 (5) | −0.0066 (5) | −0.0047 (5) |
C11 | 0.0408 (7) | 0.0481 (8) | 0.0369 (7) | −0.0140 (6) | −0.0080 (6) | −0.0078 (6) |
C12 | 0.0553 (9) | 0.0543 (9) | 0.0347 (7) | −0.0139 (7) | −0.0145 (6) | −0.0088 (6) |
C13 | 0.0572 (9) | 0.0460 (8) | 0.0302 (7) | −0.0050 (7) | −0.0050 (6) | −0.0054 (6) |
C14 | 0.0421 (8) | 0.0615 (10) | 0.0356 (7) | −0.0105 (7) | 0.0009 (6) | −0.0048 (6) |
C15 | 0.0356 (7) | 0.0516 (8) | 0.0341 (7) | −0.0112 (6) | −0.0052 (5) | −0.0058 (6) |
C16 | 0.0831 (13) | 0.0786 (13) | 0.0306 (8) | −0.0110 (10) | −0.0025 (8) | −0.0086 (8) |
C1—O1 | 1.2304 (15) | C8—C9 | 1.4026 (18) |
C1—C2 | 1.4638 (17) | C8—H8 | 0.9400 |
C1—C9 | 1.4719 (17) | C10—C15 | 1.3947 (18) |
C2—C3 | 1.3497 (16) | C10—C11 | 1.3974 (18) |
C2—C10 | 1.4840 (17) | C11—C12 | 1.386 (2) |
C3—O2 | 1.3544 (15) | C11—H11 | 0.9400 |
C3—H3 | 0.9400 | C12—C13 | 1.385 (2) |
O2—C4 | 1.3699 (15) | C12—H12 | 0.9400 |
C4—C9 | 1.3865 (16) | C13—C14 | 1.388 (2) |
C4—C5 | 1.3919 (17) | C13—C16 | 1.512 (2) |
C5—C6 | 1.376 (2) | C14—C15 | 1.3866 (19) |
C5—H5 | 0.9400 | C14—H14 | 0.9400 |
C6—C7 | 1.397 (2) | C15—H15 | 0.9400 |
C6—H6 | 0.9400 | C16—H16A | 0.9700 |
C7—C8 | 1.374 (2) | C16—H16B | 0.9700 |
C7—H7 | 0.9400 | C16—H16C | 0.9700 |
O1—C1—C2 | 124.34 (12) | C4—C9—C1 | 121.04 (11) |
O1—C1—C9 | 120.97 (12) | C8—C9—C1 | 121.16 (11) |
C2—C1—C9 | 114.68 (10) | C15—C10—C11 | 117.53 (12) |
C3—C2—C1 | 118.45 (11) | C15—C10—C2 | 120.11 (11) |
C3—C2—C10 | 118.92 (11) | C11—C10—C2 | 122.36 (12) |
C1—C2—C10 | 122.62 (10) | C12—C11—C10 | 120.57 (13) |
C2—C3—O2 | 126.36 (11) | C12—C11—H11 | 119.7 |
C2—C3—H3 | 116.8 | C10—C11—H11 | 119.7 |
O2—C3—H3 | 116.8 | C13—C12—C11 | 121.94 (13) |
C3—O2—C4 | 118.06 (9) | C13—C12—H12 | 119.0 |
O2—C4—C9 | 121.22 (11) | C11—C12—H12 | 119.0 |
O2—C4—C5 | 116.67 (11) | C12—C13—C14 | 117.48 (13) |
C9—C4—C5 | 122.11 (12) | C12—C13—C16 | 121.51 (15) |
C6—C5—C4 | 118.67 (12) | C14—C13—C16 | 121.00 (15) |
C6—C5—H5 | 120.7 | C15—C14—C13 | 121.28 (14) |
C4—C5—H5 | 120.7 | C15—C14—H14 | 119.4 |
C5—C6—C7 | 120.67 (13) | C13—C14—H14 | 119.4 |
C5—C6—H6 | 119.7 | C14—C15—C10 | 121.18 (13) |
C7—C6—H6 | 119.7 | C14—C15—H15 | 119.4 |
C8—C7—C6 | 119.77 (13) | C10—C15—H15 | 119.4 |
C8—C7—H7 | 120.1 | C13—C16—H16A | 109.5 |
C6—C7—H7 | 120.1 | C13—C16—H16B | 109.5 |
C7—C8—C9 | 120.98 (12) | H16A—C16—H16B | 109.5 |
C7—C8—H8 | 119.5 | C13—C16—H16C | 109.5 |
C9—C8—H8 | 119.5 | H16A—C16—H16C | 109.5 |
C4—C9—C8 | 117.77 (12) | H16B—C16—H16C | 109.5 |
O1—C1—C2—C3 | 177.41 (13) | C7—C8—C9—C1 | 176.44 (12) |
C9—C1—C2—C3 | −3.73 (16) | O1—C1—C9—C4 | 179.50 (12) |
O1—C1—C2—C10 | −4.05 (19) | C2—C1—C9—C4 | 0.59 (16) |
C9—C1—C2—C10 | 174.81 (10) | O1—C1—C9—C8 | 1.32 (18) |
C1—C2—C3—O2 | 3.58 (19) | C2—C1—C9—C8 | −177.58 (11) |
C10—C2—C3—O2 | −175.02 (11) | C3—C2—C10—C15 | 30.64 (18) |
C2—C3—O2—C4 | 0.20 (19) | C1—C2—C10—C15 | −147.90 (13) |
C3—O2—C4—C9 | −3.63 (17) | C3—C2—C10—C11 | −149.10 (13) |
C3—O2—C4—C5 | 176.38 (11) | C1—C2—C10—C11 | 32.37 (19) |
O2—C4—C5—C6 | −179.99 (12) | C15—C10—C11—C12 | −0.6 (2) |
C9—C4—C5—C6 | 0.01 (19) | C2—C10—C11—C12 | 179.13 (13) |
C4—C5—C6—C7 | −1.0 (2) | C10—C11—C12—C13 | −0.7 (2) |
C5—C6—C7—C8 | 0.6 (2) | C11—C12—C13—C14 | 0.7 (2) |
C6—C7—C8—C9 | 0.8 (2) | C11—C12—C13—C16 | −179.92 (16) |
O2—C4—C9—C8 | −178.63 (11) | C12—C13—C14—C15 | 0.5 (2) |
C5—C4—C9—C8 | 1.36 (18) | C16—C13—C14—C15 | −178.87 (15) |
O2—C4—C9—C1 | 3.14 (18) | C13—C14—C15—C10 | −1.8 (2) |
C5—C4—C9—C1 | −176.87 (11) | C11—C10—C15—C14 | 1.8 (2) |
C7—C8—C9—C4 | −1.79 (19) | C2—C10—C15—C14 | −177.94 (13) |
D—H···A | D—H | H···A | D···A | D—H···A |
C15—H15···O1i | 0.94 | 2.49 | 3.4255 (16) | 172 |
Symmetry code: (i) x−1, y, z. |
Funding information
The authors acknowledge financial support from Dongduk Women's University, Republic of Korea.
References
Ahn, S, Sung, J., Lee, J. H., Yoo, M., Lim, Y., Shin, S. Y. & Koh, D. (2020). Crystals, 10, 413. CrossRef Google Scholar
Bruker (2012). APEX2, SAINT and SADABS. Bruker AXS Inc. Madison, Wisconsin, USA. Google Scholar
Chang, H. C. & Doerge, D. R. (2000). Toxicol. Appl. Pharmacol. 168, 244–252. CrossRef PubMed CAS Google Scholar
Messina, M. & Hilakivi-Clarke, L. (2009). Nutr. Cancer, 61, 792–798. CrossRef CAS PubMed Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Shin, S. Y., Lee, Y. H., Lim, Y., Lee, H. J., Lee, J. H., Yoo, M., Ahn, S. & Koh, D. (2020). Crystals, 10, 911. CrossRef Google Scholar
Tikkanen, M. J. & Adlercreutz, H. (2000). Biochem. Pharmacol. 60, 1–5. CrossRef PubMed CAS Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar
Ye, Y.-B., Tang, X.-Y., Verbruggen, M. A. & Su, Y.-X. (2006). Eur. J. Nutr. 45, 327–334. CrossRef PubMed CAS Google Scholar
Zhan, S. & Ho, S. C. (2005). Am. J. Clin. Nutr. 81, 397–408. CrossRef PubMed CAS Google Scholar
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