organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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ISSN: 2414-3146

(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

Edited by A. J. Lough, University of Toronto, Canada (Received 14 January 2020; accepted 21 January 2020; online 24 January 2020)

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].

3D view (loading...)
[Scheme 3D1]
Chemical scheme
[Scheme 1]

Structure description

Chalcones are 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 flavonoids such as flavones, flavanones, flavonols and isoflavones (Marais et al., 2005[Marais, J. P. J., Ferreira, D. & Slade, D. (2005). Phytochemistry, 66, 2145-2176.]). 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[Zhuang, C., Zhang, W., Sheng, C., Zhang, W., Xing, C. & Miao, Z. (2017). Chem. Rev. 117, 7762-7810.]). In a continuation of our research inter­ests to prepare new chalcones that show broad range of biological activities (Gil et al., 2018[Gil, H., Koh, D., Lim, Y., Lee, Y. H. & Shin, S. Y. (2018). Bioorg. Med. Chem. Lett. 28, 2969-2975.], Park et al., 2018[Park, J., Shin, S., Koh, D., Lee, Y. H. & Lim, Y. (2018). Appl. Biol. Chem. 61, 267-272.]), the crystal structure of title compound has been determined.

The mol­ecular structure of the title compound is shown in Fig. 1[link]. 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[link]) appears to cause the C1=O1 double bond [1.239 (2) Å] to be slightly longer than the normal value (Allen et al., 1987[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.]). 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[link], Fig. 2[link]).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA 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+{\script{1\over 2}}, z-{\script{1\over 2}}].
[Figure 1]
Figure 1
The mol­ecular structure of the title compound, showing the atom-labelling scheme with displacement ellipsoids drawn at the 30% probability level. The intra­molecular hydrogen bond is shown as a dashed line.
[Figure 2]
Figure 2
Part of the crystal structure with the intra­molecular O—H⋯O hydrogen bond and weak C—H⋯O hydrogen bonds shown as dashed lines. For the sake of clarity, only the H atoms involved in hydrogen bonds are shown [symmetry codes: (i) x, −y + [{1\over 2}], z − [{1\over 2}]; (ii) x, −y + [{1\over 2}], z + [{1\over 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 refinement details are summarized in Table 2[link].

Table 2
Experimental details

Crystal data
Chemical formula C18H17FO5
Mr 332.32
Crystal system, space group Monoclinic, P21/c
Temperature (K) 223
a, b, c (Å) 15.5801 (12), 8.3414 (6), 12.1298 (8)
β (°) 97.086 (3)
V3) 1564.35 (19)
Z 4
Radiation type Mo Kα
μ (mm−1) 0.11
Crystal size (mm) 0.21 × 0.15 × 0.10
 
Data collection
Diffractometer PHOTON 100 CMOS
Absorption correction Multi-scan (SADABS; Bruker, 2012[Bruker (2012). APEX2, SAINT and SADABS, Bruker AXS Inc. Madison, Wisconsin, USA.])
Tmin, Tmax 0.706, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections 64701, 3904, 2539
Rint 0.079
(sin θ/λ)max−1) 0.668
 
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.048, 0.125, 1.01
No. of reflections 3904
No. of parameters 221
H-atom treatment H-atom parameters constrained
Δρmax, Δρmin (e Å−3) 0.21, −0.21
Computer programs: APEX2 and SAINT (Bruker, 2012[Bruker (2012). APEX2, SAINT and SADABS, Bruker AXS Inc. Madison, Wisconsin, USA.]), SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]), SHELXL2014 (Sheldrick, 2015[Sheldrick, G. M. (2015). Acta Cryst. C71, 3-8.]), OLEX2 (Dolomanov et al., 2009[Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2009). J. Appl. Cryst. 42, 339-341.]) and publCIF (Westrip, 2010[Westrip, S. P. (2010). J. Appl. Cryst. 43, 920-925.]).

Structural data


Computing details top

Data collection: APEX2 (Bruker, 2012); cell refinement: 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).

(E)-1-(4-Fluoro-2-hydroxyphenyl)-3-(2,3,4-trimethoxyphenyl)prop-2-en-1-one top
Crystal data top
C18H17FO5F(000) = 696
Mr = 332.32Dx = 1.411 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 15.5801 (12) ÅCell parameters from 9964 reflections
b = 8.3414 (6) Åθ = 2.8–25.8°
c = 12.1298 (8) ŵ = 0.11 mm1
β = 97.086 (3)°T = 223 K
V = 1564.35 (19) Å3Block, yellow
Z = 40.21 × 0.15 × 0.10 mm
Data collection top
PHOTON 100 CMOS
diffractometer
2539 reflections with I > 2σ(I)
φ and ω scansRint = 0.079
Absorption correction: multi-scan
(SADABS; Bruker, 2012)
θmax = 28.4°, θmin = 2.6°
Tmin = 0.706, Tmax = 0.746h = 2020
64701 measured reflectionsk = 1111
3904 independent reflectionsl = 1616
Refinement top
Refinement on F20 restraints
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.048H-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 reflectionsΔρmax = 0.21 e Å3
221 parametersΔρmin = 0.21 e Å3
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O10.92429 (10)0.0434 (2)0.67173 (13)0.0787 (5)
C10.95147 (12)0.1327 (2)0.60215 (15)0.0465 (4)
C20.89787 (11)0.1589 (2)0.49622 (15)0.0448 (4)
H20.91780.22470.44180.054*
C30.82032 (11)0.0890 (2)0.47693 (15)0.0433 (4)
H30.80310.02970.53630.052*
C40.75915 (10)0.0924 (2)0.37646 (14)0.0406 (4)
C50.67961 (11)0.01064 (19)0.37400 (14)0.0387 (4)
C60.62259 (10)0.00211 (19)0.27734 (14)0.0384 (4)
C70.64306 (11)0.0776 (2)0.18080 (15)0.0415 (4)
C80.71985 (12)0.1619 (2)0.18280 (16)0.0487 (4)
H80.73340.21440.11860.058*
C90.77632 (11)0.1685 (2)0.27966 (15)0.0473 (4)
H90.82810.22630.28020.057*
O20.65803 (8)0.04848 (15)0.47252 (10)0.0482 (3)
C100.63936 (14)0.2150 (2)0.47998 (17)0.0563 (5)
H10A0.58930.24130.42750.084*
H10B0.62740.24000.55470.084*
H10C0.68870.27700.46290.084*
O30.54649 (7)0.08295 (14)0.27272 (10)0.0439 (3)
C110.47618 (11)0.0049 (2)0.30660 (18)0.0553 (5)
H11A0.48840.03070.38490.083*
H11B0.42390.05910.29420.083*
H11C0.46820.10320.26380.083*
O40.58278 (8)0.06284 (15)0.09020 (10)0.0483 (3)
C120.59864 (13)0.1441 (2)0.00904 (16)0.0544 (5)
H12A0.60380.25830.00540.082*
H12B0.55100.12480.06690.082*
H12C0.65190.10450.03300.082*
C131.03648 (11)0.2090 (2)0.62893 (14)0.0396 (4)
C141.08778 (12)0.1692 (2)0.72906 (14)0.0458 (4)
C151.16780 (12)0.2411 (2)0.75754 (16)0.0520 (5)
H151.20270.21360.82370.062*
C161.19430 (12)0.3521 (2)0.68738 (17)0.0524 (5)
C171.14761 (12)0.3949 (2)0.58816 (17)0.0511 (5)
H171.16870.47170.54150.061*
C181.06905 (11)0.3214 (2)0.55947 (15)0.0444 (4)
H181.03640.34740.49140.053*
O51.06213 (10)0.06119 (19)0.80053 (11)0.0663 (4)
H51.01180.03250.77890.099*
F11.27125 (7)0.42519 (16)0.71683 (12)0.0763 (4)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0693 (10)0.1025 (13)0.0620 (9)0.0386 (9)0.0006 (7)0.0286 (9)
C10.0466 (10)0.0478 (10)0.0461 (10)0.0059 (8)0.0095 (8)0.0009 (8)
C20.0420 (10)0.0458 (10)0.0476 (10)0.0037 (8)0.0097 (8)0.0011 (8)
C30.0438 (10)0.0410 (9)0.0466 (10)0.0025 (8)0.0109 (8)0.0047 (8)
C40.0382 (9)0.0350 (9)0.0497 (10)0.0018 (7)0.0098 (7)0.0059 (7)
C50.0398 (9)0.0323 (8)0.0457 (9)0.0000 (7)0.0116 (7)0.0026 (7)
C60.0351 (8)0.0303 (8)0.0513 (10)0.0026 (7)0.0113 (7)0.0024 (7)
C70.0404 (9)0.0342 (9)0.0500 (10)0.0004 (7)0.0058 (8)0.0004 (7)
C80.0493 (11)0.0470 (10)0.0511 (11)0.0080 (8)0.0114 (8)0.0073 (8)
C90.0407 (10)0.0451 (10)0.0573 (11)0.0096 (8)0.0101 (8)0.0002 (8)
O20.0555 (8)0.0440 (7)0.0476 (7)0.0117 (6)0.0156 (6)0.0007 (6)
C100.0649 (13)0.0420 (10)0.0631 (12)0.0024 (9)0.0129 (10)0.0091 (9)
O30.0372 (6)0.0367 (6)0.0587 (8)0.0067 (5)0.0099 (5)0.0018 (5)
C110.0367 (10)0.0583 (12)0.0718 (13)0.0030 (9)0.0097 (9)0.0003 (10)
O40.0483 (7)0.0467 (7)0.0491 (7)0.0092 (6)0.0029 (6)0.0060 (6)
C120.0595 (12)0.0532 (12)0.0501 (11)0.0050 (9)0.0055 (9)0.0075 (9)
C130.0403 (9)0.0390 (9)0.0408 (9)0.0008 (7)0.0104 (7)0.0068 (7)
C140.0506 (11)0.0470 (10)0.0405 (9)0.0006 (8)0.0083 (8)0.0064 (8)
C150.0484 (11)0.0561 (12)0.0495 (10)0.0023 (9)0.0015 (9)0.0126 (9)
C160.0375 (10)0.0525 (11)0.0670 (13)0.0040 (8)0.0058 (9)0.0188 (10)
C170.0444 (10)0.0472 (10)0.0637 (12)0.0054 (8)0.0147 (9)0.0005 (9)
C180.0407 (9)0.0450 (10)0.0482 (10)0.0003 (8)0.0088 (8)0.0002 (8)
O50.0720 (10)0.0787 (10)0.0467 (8)0.0169 (8)0.0016 (7)0.0116 (7)
F10.0467 (7)0.0820 (9)0.0978 (10)0.0187 (6)0.0004 (6)0.0190 (8)
Geometric parameters (Å, º) top
O1—C11.239 (2)C10—H10C0.9700
C1—O11.239 (2)O3—C111.420 (2)
C1—C21.460 (3)C11—H11A0.9700
C1—C131.469 (2)C11—H11B0.9700
C2—C31.336 (2)C11—H11C0.9700
C2—H20.9400O4—C121.429 (2)
C3—C41.452 (2)C12—H12A0.9700
C3—H30.9400C12—H12B0.9700
C4—C91.389 (2)C12—H12C0.9700
C4—C51.412 (2)C13—C181.397 (2)
C5—O21.372 (2)C13—C141.409 (2)
C5—C61.383 (2)C14—O51.345 (2)
C6—O31.3768 (19)C14—C151.388 (3)
C6—C71.400 (2)C15—C161.356 (3)
C7—O41.360 (2)C15—H150.9400
C7—C81.386 (2)C16—F11.353 (2)
C8—C91.379 (3)C16—C171.374 (3)
C8—H80.9400C17—C181.375 (2)
C9—H90.9400C17—H170.9400
O2—C101.424 (2)C18—H180.9400
C10—H10A0.9700O5—H50.8300
C10—H10B0.9700
O1—C1—C2118.90 (17)H10B—C10—H10C109.5
O1—C1—C2118.90 (17)C6—O3—C11114.41 (13)
O1—C1—C13118.98 (17)O3—C11—H11A109.5
O1—C1—C13118.98 (17)O3—C11—H11B109.5
C2—C1—C13122.12 (16)H11A—C11—H11B109.5
C3—C2—C1119.70 (17)O3—C11—H11C109.5
C3—C2—H2120.2H11A—C11—H11C109.5
C1—C2—H2120.2H11B—C11—H11C109.5
C2—C3—C4128.64 (17)C7—O4—C12117.62 (13)
C2—C3—H3115.7O4—C12—H12A109.5
C4—C3—H3115.7O4—C12—H12B109.5
C9—C4—C5117.57 (16)H12A—C12—H12B109.5
C9—C4—C3122.92 (15)O4—C12—H12C109.5
C5—C4—C3119.47 (16)H12A—C12—H12C109.5
O2—C5—C6121.26 (15)H12B—C12—H12C109.5
O2—C5—C4117.64 (15)C18—C13—C14117.93 (16)
C6—C5—C4120.89 (15)C18—C13—C1122.82 (16)
O3—C6—C5121.40 (15)C14—C13—C1119.25 (16)
O3—C6—C7118.78 (15)O5—C14—C15117.28 (17)
C5—C6—C7119.80 (15)O5—C14—C13122.11 (16)
O4—C7—C8124.65 (16)C15—C14—C13120.61 (17)
O4—C7—C6115.41 (14)C16—C15—C14118.20 (18)
C8—C7—C6119.93 (16)C16—C15—H15120.9
C9—C8—C7119.58 (17)C14—C15—H15120.9
C9—C8—H8120.2F1—C16—C15118.06 (18)
C7—C8—H8120.2F1—C16—C17118.05 (19)
C8—C9—C4122.19 (16)C15—C16—C17123.89 (17)
C8—C9—H9118.9C16—C17—C18117.68 (18)
C4—C9—H9118.9C16—C17—H17121.2
C5—O2—C10118.67 (14)C18—C17—H17121.2
O2—C10—H10A109.5C17—C18—C13121.66 (18)
O2—C10—H10B109.5C17—C18—H18119.2
H10A—C10—H10B109.5C13—C18—H18119.2
O2—C10—H10C109.5C14—O5—H5109.5
H10A—C10—H10C109.5
O1—O1—C1—C20.0 (2)C6—C5—O2—C1061.3 (2)
O1—O1—C1—C130.0 (3)C4—C5—O2—C10123.86 (17)
O1—C1—C2—C31.2 (3)C5—C6—O3—C1186.36 (19)
O1—C1—C2—C31.2 (3)C7—C6—O3—C1195.34 (19)
C13—C1—C2—C3178.72 (16)C8—C7—O4—C121.9 (2)
C1—C2—C3—C4176.61 (17)C6—C7—O4—C12177.06 (15)
C2—C3—C4—C93.0 (3)O1—C1—C13—C18174.58 (19)
C2—C3—C4—C5179.42 (17)O1—C1—C13—C18174.58 (19)
C9—C4—C5—O2172.57 (15)C2—C1—C13—C185.3 (3)
C3—C4—C5—O29.7 (2)O1—C1—C13—C144.9 (3)
C9—C4—C5—C62.3 (2)O1—C1—C13—C144.9 (3)
C3—C4—C5—C6175.44 (15)C2—C1—C13—C14175.23 (16)
O2—C5—C6—O38.1 (2)C18—C13—C14—O5179.35 (16)
C4—C5—C6—O3177.25 (14)C1—C13—C14—O51.1 (3)
O2—C5—C6—C7173.64 (15)C18—C13—C14—C150.5 (3)
C4—C5—C6—C71.0 (2)C1—C13—C14—C15178.97 (16)
O3—C6—C7—O41.9 (2)O5—C14—C15—C16179.04 (17)
C5—C6—C7—O4179.78 (14)C13—C14—C15—C161.1 (3)
O3—C6—C7—C8179.05 (15)C14—C15—C16—F1178.23 (16)
C5—C6—C7—C80.7 (2)C14—C15—C16—C171.7 (3)
O4—C7—C8—C9179.89 (16)F1—C16—C17—C18179.28 (16)
C6—C7—C8—C91.1 (3)C15—C16—C17—C180.7 (3)
C7—C8—C9—C40.2 (3)C16—C17—C18—C131.0 (3)
C5—C4—C9—C81.9 (3)C14—C13—C18—C171.6 (3)
C3—C4—C9—C8175.76 (17)C1—C13—C18—C17177.87 (17)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O5—H5···O10.831.772.499 (2)146
C18—H18···O5i0.942.523.279 (2)138
Symmetry code: (i) x, y+1/2, z1/2.
 

Funding information

The authors acknowledge financial support from the Basic Science Research Program (award No. NRF-2019R1F1A1058747).

References

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