organic compounds
(E)-1-(4-Fluoro-2-hydroxyphenyl)-3-(2,3,4-trimethoxyphenyl)prop-2-en-1-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 molecule, C18H17FO5, the conformation about the C=C bond of the central enone group is trans. The dihedral angle between the benzene rings is 13.08 (3)°. The hydroxy group attached to the benzene ring is involved in an intramolecular O—H⋯O hydrogen bond. In the crystal, weak C—H⋯O hydrogen bonds link the molecules into chains along [001].
Keywords: crystal structure; chalcone; C—H⋯O hydrogen bonds; dihedral angle.
CCDC reference: 1979111
Structure description
α,β-unsaturated carbonyl (enone) compounds, which connect two aromatic rings. Especially when they have a hydroxyl group at the ortho position of an aromatic ring adjacent to the carbonyl group, they play important roles as precursors to form other such as flavones, flavanones, flavonols and isoflavones (Marais et al., 2005). A variety of chlacones have been isolated from natural sources and synthesized because they have shown wide spectrum of biological activities against various diseases according to a recent review (Zhuang et al., 2017). In a continuation of our research interests to prepare new that show broad range of biological activities (Gil et al., 2018, Park et al., 2018), the of title compound has been determined.
areThe molecular structure of the title compound is shown in Fig. 1. In the central enone group, the trans configuration of the C2=C3 double bond is confirmed by the C1—C2=C3—C4 torsion angle of −176.6 (2)°. An intramolecular O5—H5⋯O1 hydrogen bond (Table 1) appears to cause the C1=O1 double bond [1.239 (2) Å] to be slightly longer than the normal value (Allen et al., 1987). The dihedral angle between the two benzene rings is 13.08 (3)°. Among the methoxy groups attached to the C4 benzene ring, the methoxy group at the meta position is almost perpendicular to the benzene ring [C5—C6—O3—C11 = 86.3 (2)°] and the para methoxy group is almost coplanar with the ring [C6—C7—O4—C12 = 177.1 (2)°]. The methoxy group at the ortho position is rotated significantly from the ring plane [C4—C5—O2—C10 = −123.9 (2)°]. In the crystal, weak C—H⋯O hydrogen bonds link the molecules into chains propagating along [001] (Table 1, Fig. 2).
Synthesis and crystallization
To a solution of 1-(4-fluoro-2-hydroxyphenyl)ethanone (309 mg, 2 mmol) in 40 ml of anhydrous ethanol was added 2,3,4-trimethoxybenzaldehyde (392 mg, 2 mmol) and the temperature was adjusted to around 275–277 K in an ice bath. To the cooled reaction mixture was added 3 ml of 40% aqueous KOH solution and the reaction mixture was stirred at room temperature for 20 h. After completion of the reaction (monitored by thin-layer chromatography), this mixture was poured into ice water (100 ml) and the resulting solution acidified with 6 N HCl solution until pH = 3 to produce a solid product. This solid was recrystallized from an ethanol solution to obtain single crystals of the title compound in 54% yield.
Refinement
Crystal data, data collection and structure .
details are summarized in Table 2Structural data
CCDC reference: 1979111
https://doi.org/10.1107/S2414314620000711/lh4051sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314620000711/lh4051Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S2414314620000711/lh4051Isup3.cml
Data collection: APEX2 (Bruker, 2012); cell
SAINT (Bruker, 2012); data reduction: SAINT (Bruker, 2012); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: publCIF (Westrip, 2010).C18H17FO5 | F(000) = 696 |
Mr = 332.32 | Dx = 1.411 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 15.5801 (12) Å | Cell parameters from 9964 reflections |
b = 8.3414 (6) Å | θ = 2.8–25.8° |
c = 12.1298 (8) Å | µ = 0.11 mm−1 |
β = 97.086 (3)° | T = 223 K |
V = 1564.35 (19) Å3 | Block, yellow |
Z = 4 | 0.21 × 0.15 × 0.10 mm |
PHOTON 100 CMOS diffractometer | 2539 reflections with I > 2σ(I) |
φ and ω scans | Rint = 0.079 |
Absorption correction: multi-scan (SADABS; Bruker, 2012) | θmax = 28.4°, θmin = 2.6° |
Tmin = 0.706, Tmax = 0.746 | h = −20→20 |
64701 measured reflections | k = −11→11 |
3904 independent reflections | l = −16→16 |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.048 | H-atom parameters constrained |
wR(F2) = 0.125 | w = 1/[σ2(Fo2) + (0.0473P)2 + 0.6183P] where P = (Fo2 + 2Fc2)/3 |
S = 1.01 | (Δ/σ)max = 0.001 |
3904 reflections | Δρmax = 0.21 e Å−3 |
221 parameters | Δρmin = −0.21 e Å−3 |
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 | ||
O1 | 0.92429 (10) | 0.0434 (2) | 0.67173 (13) | 0.0787 (5) | |
C1 | 0.95147 (12) | 0.1327 (2) | 0.60215 (15) | 0.0465 (4) | |
C2 | 0.89787 (11) | 0.1589 (2) | 0.49622 (15) | 0.0448 (4) | |
H2 | 0.9178 | 0.2247 | 0.4418 | 0.054* | |
C3 | 0.82032 (11) | 0.0890 (2) | 0.47693 (15) | 0.0433 (4) | |
H3 | 0.8031 | 0.0297 | 0.5363 | 0.052* | |
C4 | 0.75915 (10) | 0.0924 (2) | 0.37646 (14) | 0.0406 (4) | |
C5 | 0.67961 (11) | 0.01064 (19) | 0.37400 (14) | 0.0387 (4) | |
C6 | 0.62259 (10) | 0.00211 (19) | 0.27734 (14) | 0.0384 (4) | |
C7 | 0.64306 (11) | 0.0776 (2) | 0.18080 (15) | 0.0415 (4) | |
C8 | 0.71985 (12) | 0.1619 (2) | 0.18280 (16) | 0.0487 (4) | |
H8 | 0.7334 | 0.2144 | 0.1186 | 0.058* | |
C9 | 0.77632 (11) | 0.1685 (2) | 0.27966 (15) | 0.0473 (4) | |
H9 | 0.8281 | 0.2263 | 0.2802 | 0.057* | |
O2 | 0.65803 (8) | −0.04848 (15) | 0.47252 (10) | 0.0482 (3) | |
C10 | 0.63936 (14) | −0.2150 (2) | 0.47998 (17) | 0.0563 (5) | |
H10A | 0.5893 | −0.2413 | 0.4275 | 0.084* | |
H10B | 0.6274 | −0.2400 | 0.5547 | 0.084* | |
H10C | 0.6887 | −0.2770 | 0.4629 | 0.084* | |
O3 | 0.54649 (7) | −0.08295 (14) | 0.27272 (10) | 0.0439 (3) | |
C11 | 0.47618 (11) | 0.0049 (2) | 0.30660 (18) | 0.0553 (5) | |
H11A | 0.4884 | 0.0307 | 0.3849 | 0.083* | |
H11B | 0.4239 | −0.0591 | 0.2942 | 0.083* | |
H11C | 0.4682 | 0.1032 | 0.2638 | 0.083* | |
O4 | 0.58278 (8) | 0.06284 (15) | 0.09020 (10) | 0.0483 (3) | |
C12 | 0.59864 (13) | 0.1441 (2) | −0.00904 (16) | 0.0544 (5) | |
H12A | 0.6038 | 0.2583 | 0.0054 | 0.082* | |
H12B | 0.5510 | 0.1248 | −0.0669 | 0.082* | |
H12C | 0.6519 | 0.1045 | −0.0330 | 0.082* | |
C13 | 1.03648 (11) | 0.2090 (2) | 0.62893 (14) | 0.0396 (4) | |
C14 | 1.08778 (12) | 0.1692 (2) | 0.72906 (14) | 0.0458 (4) | |
C15 | 1.16780 (12) | 0.2411 (2) | 0.75754 (16) | 0.0520 (5) | |
H15 | 1.2027 | 0.2136 | 0.8237 | 0.062* | |
C16 | 1.19430 (12) | 0.3521 (2) | 0.68738 (17) | 0.0524 (5) | |
C17 | 1.14761 (12) | 0.3949 (2) | 0.58816 (17) | 0.0511 (5) | |
H17 | 1.1687 | 0.4717 | 0.5415 | 0.061* | |
C18 | 1.06905 (11) | 0.3214 (2) | 0.55947 (15) | 0.0444 (4) | |
H18 | 1.0364 | 0.3474 | 0.4914 | 0.053* | |
O5 | 1.06213 (10) | 0.06119 (19) | 0.80053 (11) | 0.0663 (4) | |
H5 | 1.0118 | 0.0325 | 0.7789 | 0.099* | |
F1 | 1.27125 (7) | 0.42519 (16) | 0.71683 (12) | 0.0763 (4) |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0693 (10) | 0.1025 (13) | 0.0620 (9) | −0.0386 (9) | −0.0006 (7) | 0.0286 (9) |
C1 | 0.0466 (10) | 0.0478 (10) | 0.0461 (10) | −0.0059 (8) | 0.0095 (8) | −0.0009 (8) |
C2 | 0.0420 (10) | 0.0458 (10) | 0.0476 (10) | −0.0037 (8) | 0.0097 (8) | −0.0011 (8) |
C3 | 0.0438 (10) | 0.0410 (9) | 0.0466 (10) | −0.0025 (8) | 0.0109 (8) | −0.0047 (8) |
C4 | 0.0382 (9) | 0.0350 (9) | 0.0497 (10) | −0.0018 (7) | 0.0098 (7) | −0.0059 (7) |
C5 | 0.0398 (9) | 0.0323 (8) | 0.0457 (9) | 0.0000 (7) | 0.0116 (7) | −0.0026 (7) |
C6 | 0.0351 (8) | 0.0303 (8) | 0.0513 (10) | −0.0026 (7) | 0.0113 (7) | −0.0024 (7) |
C7 | 0.0404 (9) | 0.0342 (9) | 0.0500 (10) | −0.0004 (7) | 0.0058 (8) | −0.0004 (7) |
C8 | 0.0493 (11) | 0.0470 (10) | 0.0511 (11) | −0.0080 (8) | 0.0114 (8) | 0.0073 (8) |
C9 | 0.0407 (10) | 0.0451 (10) | 0.0573 (11) | −0.0096 (8) | 0.0101 (8) | −0.0002 (8) |
O2 | 0.0555 (8) | 0.0440 (7) | 0.0476 (7) | −0.0117 (6) | 0.0156 (6) | −0.0007 (6) |
C10 | 0.0649 (13) | 0.0420 (10) | 0.0631 (12) | 0.0024 (9) | 0.0129 (10) | 0.0091 (9) |
O3 | 0.0372 (6) | 0.0367 (6) | 0.0587 (8) | −0.0067 (5) | 0.0099 (5) | −0.0018 (5) |
C11 | 0.0367 (10) | 0.0583 (12) | 0.0718 (13) | 0.0030 (9) | 0.0097 (9) | 0.0003 (10) |
O4 | 0.0483 (7) | 0.0467 (7) | 0.0491 (7) | −0.0092 (6) | 0.0029 (6) | 0.0060 (6) |
C12 | 0.0595 (12) | 0.0532 (12) | 0.0501 (11) | −0.0050 (9) | 0.0055 (9) | 0.0075 (9) |
C13 | 0.0403 (9) | 0.0390 (9) | 0.0408 (9) | −0.0008 (7) | 0.0104 (7) | −0.0068 (7) |
C14 | 0.0506 (11) | 0.0470 (10) | 0.0405 (9) | −0.0006 (8) | 0.0083 (8) | −0.0064 (8) |
C15 | 0.0484 (11) | 0.0561 (12) | 0.0495 (10) | 0.0023 (9) | −0.0015 (9) | −0.0126 (9) |
C16 | 0.0375 (10) | 0.0525 (11) | 0.0670 (13) | −0.0040 (8) | 0.0058 (9) | −0.0188 (10) |
C17 | 0.0444 (10) | 0.0472 (10) | 0.0637 (12) | −0.0054 (8) | 0.0147 (9) | −0.0005 (9) |
C18 | 0.0407 (9) | 0.0450 (10) | 0.0482 (10) | −0.0003 (8) | 0.0088 (8) | −0.0002 (8) |
O5 | 0.0720 (10) | 0.0787 (10) | 0.0467 (8) | −0.0169 (8) | 0.0016 (7) | 0.0116 (7) |
F1 | 0.0467 (7) | 0.0820 (9) | 0.0978 (10) | −0.0187 (6) | −0.0004 (6) | −0.0190 (8) |
O1—C1 | 1.239 (2) | C10—H10C | 0.9700 |
C1—O1 | 1.239 (2) | O3—C11 | 1.420 (2) |
C1—C2 | 1.460 (3) | C11—H11A | 0.9700 |
C1—C13 | 1.469 (2) | C11—H11B | 0.9700 |
C2—C3 | 1.336 (2) | C11—H11C | 0.9700 |
C2—H2 | 0.9400 | O4—C12 | 1.429 (2) |
C3—C4 | 1.452 (2) | C12—H12A | 0.9700 |
C3—H3 | 0.9400 | C12—H12B | 0.9700 |
C4—C9 | 1.389 (2) | C12—H12C | 0.9700 |
C4—C5 | 1.412 (2) | C13—C18 | 1.397 (2) |
C5—O2 | 1.372 (2) | C13—C14 | 1.409 (2) |
C5—C6 | 1.383 (2) | C14—O5 | 1.345 (2) |
C6—O3 | 1.3768 (19) | C14—C15 | 1.388 (3) |
C6—C7 | 1.400 (2) | C15—C16 | 1.356 (3) |
C7—O4 | 1.360 (2) | C15—H15 | 0.9400 |
C7—C8 | 1.386 (2) | C16—F1 | 1.353 (2) |
C8—C9 | 1.379 (3) | C16—C17 | 1.374 (3) |
C8—H8 | 0.9400 | C17—C18 | 1.375 (2) |
C9—H9 | 0.9400 | C17—H17 | 0.9400 |
O2—C10 | 1.424 (2) | C18—H18 | 0.9400 |
C10—H10A | 0.9700 | O5—H5 | 0.8300 |
C10—H10B | 0.9700 | ||
O1—C1—C2 | 118.90 (17) | H10B—C10—H10C | 109.5 |
O1—C1—C2 | 118.90 (17) | C6—O3—C11 | 114.41 (13) |
O1—C1—C13 | 118.98 (17) | O3—C11—H11A | 109.5 |
O1—C1—C13 | 118.98 (17) | O3—C11—H11B | 109.5 |
C2—C1—C13 | 122.12 (16) | H11A—C11—H11B | 109.5 |
C3—C2—C1 | 119.70 (17) | O3—C11—H11C | 109.5 |
C3—C2—H2 | 120.2 | H11A—C11—H11C | 109.5 |
C1—C2—H2 | 120.2 | H11B—C11—H11C | 109.5 |
C2—C3—C4 | 128.64 (17) | C7—O4—C12 | 117.62 (13) |
C2—C3—H3 | 115.7 | O4—C12—H12A | 109.5 |
C4—C3—H3 | 115.7 | O4—C12—H12B | 109.5 |
C9—C4—C5 | 117.57 (16) | H12A—C12—H12B | 109.5 |
C9—C4—C3 | 122.92 (15) | O4—C12—H12C | 109.5 |
C5—C4—C3 | 119.47 (16) | H12A—C12—H12C | 109.5 |
O2—C5—C6 | 121.26 (15) | H12B—C12—H12C | 109.5 |
O2—C5—C4 | 117.64 (15) | C18—C13—C14 | 117.93 (16) |
C6—C5—C4 | 120.89 (15) | C18—C13—C1 | 122.82 (16) |
O3—C6—C5 | 121.40 (15) | C14—C13—C1 | 119.25 (16) |
O3—C6—C7 | 118.78 (15) | O5—C14—C15 | 117.28 (17) |
C5—C6—C7 | 119.80 (15) | O5—C14—C13 | 122.11 (16) |
O4—C7—C8 | 124.65 (16) | C15—C14—C13 | 120.61 (17) |
O4—C7—C6 | 115.41 (14) | C16—C15—C14 | 118.20 (18) |
C8—C7—C6 | 119.93 (16) | C16—C15—H15 | 120.9 |
C9—C8—C7 | 119.58 (17) | C14—C15—H15 | 120.9 |
C9—C8—H8 | 120.2 | F1—C16—C15 | 118.06 (18) |
C7—C8—H8 | 120.2 | F1—C16—C17 | 118.05 (19) |
C8—C9—C4 | 122.19 (16) | C15—C16—C17 | 123.89 (17) |
C8—C9—H9 | 118.9 | C16—C17—C18 | 117.68 (18) |
C4—C9—H9 | 118.9 | C16—C17—H17 | 121.2 |
C5—O2—C10 | 118.67 (14) | C18—C17—H17 | 121.2 |
O2—C10—H10A | 109.5 | C17—C18—C13 | 121.66 (18) |
O2—C10—H10B | 109.5 | C17—C18—H18 | 119.2 |
H10A—C10—H10B | 109.5 | C13—C18—H18 | 119.2 |
O2—C10—H10C | 109.5 | C14—O5—H5 | 109.5 |
H10A—C10—H10C | 109.5 | ||
O1—O1—C1—C2 | 0.0 (2) | C6—C5—O2—C10 | 61.3 (2) |
O1—O1—C1—C13 | 0.0 (3) | C4—C5—O2—C10 | −123.86 (17) |
O1—C1—C2—C3 | 1.2 (3) | C5—C6—O3—C11 | 86.36 (19) |
O1—C1—C2—C3 | 1.2 (3) | C7—C6—O3—C11 | −95.34 (19) |
C13—C1—C2—C3 | −178.72 (16) | C8—C7—O4—C12 | −1.9 (2) |
C1—C2—C3—C4 | −176.61 (17) | C6—C7—O4—C12 | 177.06 (15) |
C2—C3—C4—C9 | 3.0 (3) | O1—C1—C13—C18 | −174.58 (19) |
C2—C3—C4—C5 | −179.42 (17) | O1—C1—C13—C18 | −174.58 (19) |
C9—C4—C5—O2 | −172.57 (15) | C2—C1—C13—C18 | 5.3 (3) |
C3—C4—C5—O2 | 9.7 (2) | O1—C1—C13—C14 | 4.9 (3) |
C9—C4—C5—C6 | 2.3 (2) | O1—C1—C13—C14 | 4.9 (3) |
C3—C4—C5—C6 | −175.44 (15) | C2—C1—C13—C14 | −175.23 (16) |
O2—C5—C6—O3 | −8.1 (2) | C18—C13—C14—O5 | −179.35 (16) |
C4—C5—C6—O3 | 177.25 (14) | C1—C13—C14—O5 | 1.1 (3) |
O2—C5—C6—C7 | 173.64 (15) | C18—C13—C14—C15 | 0.5 (3) |
C4—C5—C6—C7 | −1.0 (2) | C1—C13—C14—C15 | −178.97 (16) |
O3—C6—C7—O4 | 1.9 (2) | O5—C14—C15—C16 | −179.04 (17) |
C5—C6—C7—O4 | −179.78 (14) | C13—C14—C15—C16 | 1.1 (3) |
O3—C6—C7—C8 | −179.05 (15) | C14—C15—C16—F1 | 178.23 (16) |
C5—C6—C7—C8 | −0.7 (2) | C14—C15—C16—C17 | −1.7 (3) |
O4—C7—C8—C9 | −179.89 (16) | F1—C16—C17—C18 | −179.28 (16) |
C6—C7—C8—C9 | 1.1 (3) | C15—C16—C17—C18 | 0.7 (3) |
C7—C8—C9—C4 | 0.2 (3) | C16—C17—C18—C13 | 1.0 (3) |
C5—C4—C9—C8 | −1.9 (3) | C14—C13—C18—C17 | −1.6 (3) |
C3—C4—C9—C8 | 175.76 (17) | C1—C13—C18—C17 | 177.87 (17) |
D—H···A | D—H | H···A | D···A | D—H···A |
O5—H5···O1 | 0.83 | 1.77 | 2.499 (2) | 146 |
C18—H18···O5i | 0.94 | 2.52 | 3.279 (2) | 138 |
Symmetry code: (i) x, −y+1/2, z−1/2. |
Funding information
The authors acknowledge financial support from the Basic Science Research Program (award No. NRF-2019R1F1A1058747).
References
Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–S19. CrossRef Web of Science Google Scholar
Bruker (2012). APEX2, SAINT and SADABS, Bruker AXS Inc. Madison, Wisconsin, USA. Google Scholar
Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2009). J. Appl. Cryst. 42, 339–341. Web of Science CrossRef CAS IUCr Journals Google Scholar
Gil, H., Koh, D., Lim, Y., Lee, Y. H. & Shin, S. Y. (2018). Bioorg. Med. Chem. Lett. 28, 2969–2975. CrossRef CAS PubMed Google Scholar
Marais, J. P. J., Ferreira, D. & Slade, D. (2005). Phytochemistry, 66, 2145–2176. Web of Science CrossRef PubMed CAS Google Scholar
Park, J., Shin, S., Koh, D., Lee, Y. H. & Lim, Y. (2018). Appl. Biol. Chem. 61, 267–272. CrossRef CAS 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
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar
Zhuang, C., Zhang, W., Sheng, C., Zhang, W., Xing, C. & Miao, Z. (2017). Chem. Rev. 117, 7762–7810. Web of Science CrossRef CAS PubMed Google Scholar
This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.