organic compounds
(E)-3-(2,5-Difluorophenyl)-1-phenylprop-2-en-1-one
aDepartamento de Química, Instituto de Ciências Exatas, Universidade Federal Rural do Rio de Janeiro, 23851-970 Seropédica, RJ, Brazil, bUniversidade Federal Fluminense, Instituto de Física, Lab LDRX-UFF, 24210-346 Niterói, RJ, Brazil, cUniversidade Federal Fluminense, Departamento de Química Orgânica, Programa de Pós-Graduação em Química, 24020-141 Niterói, RJ, Brazil, and dDivisão de Metrologia Química, LAMOC, Instituto Nacional de Metrologia, Qualidade e Tecnologia, INMETRO, Av. N. Sra. das Graças, 50, 25250-020 Duque de Caxias, RJ, Brazil
*Correspondence e-mail: cesarinsobrinho@gmail.com
The title chalcone derivative, C15H10F2O, is almost planar, with the benzene ring being inclined to the phenyl ring by 7.45 (9)°. The conformation about the C=C bond is E. In the crystal, molecules are linked by two pairs of C—H⋯F hydrogen bonds, forming inversion dimers enclosing R22(8) and R21(10) ring motifs. The dimers stack along the a axis with the separation of the C=C bonds being 4.2926 (4) Å.
Keywords: crystal structure; chalcone; [2 + 2] cycloaddition reactions; C—H⋯F hydrogen bonds; inversion dimers.
CCDC reference: 1498634
Structure description
Chalcone is a generic term given to compounds having the 1,3-diphenylprop-2-en-1-one moiety. They were the first isolatable compounds from flavonoid biosynthesis in plants (Bohm, 1998; Yazdan et al., 2015) and are widely distributed in fruits, vegetables, spices, tea and soy-based foodstuffs. They have interesting pharmacological properties (Di Carlos et al., 1999; Das & Manna, 2016), including analgesic, antioxidant, antifungal, antibacterial, antiprotozoal, gastric `protectant', antimutagenic, antitumorogenic, anti-inflammatory (Yadav et al., 2011) and antineurodegeneration properties (Sahu et al., 2012; Singh et al., 2014). The title chalcone derivative was obtained by a Claisen–Schimdt condensation in a basic solution of ethanol and water between 2,5-difluorobenzaldehyde and acetophenone.
The molecular structure of the title compound is illustrated in Fig. 1. The structure is almost planar, with the dihedral angle between the benzene (C1–C6) and phenyl (C10–C15) rings being 7.45 (9)°. The conformation of the keto group (C9=O1) with respect to the olefinic double bond (C7=C8) is cis. The conformation about the C7=C8 bond itself is E, with the 2,5-difluorobenzene ring opposite to the phenyl ring.
In the crystal, molecules are linked by two pairs of C—H⋯F hydrogen bonds, forming inversion dimers enclosing R22(8) and R21(10) rings (Table 1 and Fig. 2). The separation distances of bonds C7=C8⋯C7i=C8i [symmetry code: (i) 1 + x, y, z] of adjacent molecules stacked along the a axis is 4.2926 (4) Å, with an angle of 52.0 (1)° (Fig. 3). This distance is in the range for relevant distances enrolled in photochemical [2 + 2] cycloaddition reactions between (Sonoda, 2011).
Synthesis and crystallization
Potassium hydroxide in 10% molar (0.0026 g ml−1) concentration relative to the ketone was added to an ethanol–water (6:1) mixture. To this solution, the total amount of 2,5-difluorobenzaldehyde (582 mg, 4.1 mmol) and half of the acetophenone (288 mg, 2.4 mmol) were added at room temperature. After approximately 1–2 h, the reminder of the acetophenone was added under constant stirring at 298 K, and the reaction was continued until the appearance of a yellow precipitate. The reaction mixture was filtered and the solid residue obtained was washed with cold water until a neutral pH was attained and was then recrystallized a number of times from a mixture of ethanol and water (yield 65%, m.p. 361–363 K). Yellow single crystals suitable for X-ray diffraction were obtained by slow evaporation of an ethanol solution of the title compound (m.p. 363 K). Spectroscopic data: IR (KBr) ν (cm−1): 1674.3 (C=O s-cis); 1655.0 (C=O s-trans); 1610.9 (C=C s-cis). 1H NMR (500 MHz, CDCl3): δ 7.90–6.50 (m, 8H, aromatic); 7.83 (d, H7); 7.59 (d, H8). 13C NMR (125 MHz, CDCl3): δ 198.8 (C=O); 160.5 (dd, C2); 155.0 (dd, C5); 137.6 (C10); 135.9 (C7); 133.0 (C13); 128.6 (C14=C12); 128.5 (C15=C11); 125.3 (C8); 118.5 (d, C3); 117.9 (d, C4); 117.2 (d, C1). (MS m/z (%): 244 (M+., 100); 243 (29); 225 (36); 215 (18); 214 (5); 201 (7); 196 (11); 195 (6); 167 (42); 139 (29); 119 (36); 105 (67); 77 (82).
Refinement
Crystal data, data collection and structure .
details are summarized in Table 2Structural data
CCDC reference: 1498634
10.1107/S2414314616012955/su4068sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S2414314616012955/su4068Isup2.hkl
Supporting information file. DOI: 10.1107/S2414314616012955/su4068Isup3.cml
Data collection: SAINT (Bruker, 2015); cell
APEX3 (Bruker, 2015); data reduction: SAINT (Bruker, 2015); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: SHELXTL (Sheldrick, 2008) and Mercury (Macrae et al., 2008); software used to prepare material for publication: WinGX (Farrugia, 2012), SHELXL2014 (Sheldrick, 2015) and PLATON (Spek, 2009).C15H10F2O | F(000) = 504 |
Mr = 244.23 | Dx = 1.435 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 3798 reflections |
a = 4.2926 (4) Å | θ = 2.7–26.4° |
b = 17.7983 (13) Å | µ = 0.11 mm−1 |
c = 14.8522 (13) Å | T = 150 K |
β = 94.757 (4)° | Orthombic, colorless |
V = 1130.81 (17) Å3 | 0.31 × 0.23 × 0.16 mm |
Z = 4 |
Bruker D8 Venture diffractometer | 1740 reflections with I > 2σ(I) |
Radiation source: Microfocus sealed tube, Incoatec Iµs | Rint = 0.052 |
Quazar multilayer mirror monochromator | θmax = 26.4°, θmin = 2.3° |
φ and ω scans | h = −5→5 |
5621 measured reflections | k = −21→22 |
2322 independent reflections | l = −18→18 |
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) = 0.136 | w = 1/[σ2(Fo2) + (0.0443P)2 + 0.290P] where P = (Fo2 + 2Fc2)/3 |
S = 1.07 | (Δ/σ)max < 0.001 |
2322 reflections | Δρmax = 0.32 e Å−3 |
163 parameters | Δρmin = −0.24 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 | ||
F2 | 0.0822 (3) | 0.50588 (6) | 0.19482 (7) | 0.0330 (3) | |
F1 | 0.9771 (3) | 0.60432 (6) | 0.44588 (7) | 0.0351 (3) | |
O1 | 0.0788 (4) | 0.25342 (7) | 0.32124 (9) | 0.0367 (4) | |
C1 | 0.6528 (4) | 0.50652 (10) | 0.38831 (11) | 0.0229 (4) | |
H1 | 0.739 | 0.4748 | 0.4354 | 0.027* | |
C5 | 0.3075 (4) | 0.52985 (10) | 0.25802 (11) | 0.0234 (4) | |
C6 | 0.4238 (4) | 0.47913 (10) | 0.32404 (11) | 0.0215 (4) | |
C10 | 0.3791 (4) | 0.21865 (10) | 0.45575 (11) | 0.0230 (4) | |
C2 | 0.7518 (4) | 0.57955 (10) | 0.38272 (12) | 0.0244 (4) | |
C9 | 0.2765 (5) | 0.27205 (10) | 0.38094 (12) | 0.0254 (4) | |
C3 | 0.6369 (5) | 0.62892 (10) | 0.31648 (12) | 0.0267 (4) | |
H3 | 0.7128 | 0.679 | 0.3146 | 0.032* | |
C7 | 0.3066 (4) | 0.40188 (10) | 0.32591 (11) | 0.0241 (4) | |
H7 | 0.1368 | 0.3892 | 0.2835 | 0.029* | |
C4 | 0.4083 (4) | 0.60333 (10) | 0.25306 (12) | 0.0269 (4) | |
H4 | 0.3216 | 0.6357 | 0.2067 | 0.032* | |
C8 | 0.4166 (5) | 0.34818 (10) | 0.38147 (12) | 0.0269 (4) | |
H8 | 0.5912 | 0.3588 | 0.4231 | 0.032* | |
C15 | 0.2643 (5) | 0.14540 (11) | 0.45084 (13) | 0.0309 (5) | |
H15 | 0.1283 | 0.1304 | 0.4003 | 0.037* | |
C13 | 0.5437 (5) | 0.11552 (11) | 0.59271 (13) | 0.0330 (5) | |
H13 | 0.601 | 0.0802 | 0.6392 | 0.04* | |
C11 | 0.5791 (5) | 0.23899 (11) | 0.53030 (12) | 0.0300 (5) | |
H11 | 0.6629 | 0.2884 | 0.5342 | 0.036* | |
C14 | 0.3461 (5) | 0.09438 (11) | 0.51866 (14) | 0.0360 (5) | |
H14 | 0.2666 | 0.0446 | 0.5145 | 0.043* | |
C12 | 0.6573 (5) | 0.18811 (12) | 0.59882 (13) | 0.0362 (5) | |
H12 | 0.7893 | 0.2031 | 0.6502 | 0.043* |
U11 | U22 | U33 | U12 | U13 | U23 | |
F2 | 0.0354 (7) | 0.0304 (6) | 0.0309 (6) | 0.0010 (5) | −0.0107 (5) | 0.0019 (4) |
F1 | 0.0362 (7) | 0.0324 (6) | 0.0351 (6) | −0.0080 (5) | −0.0070 (5) | 0.0000 (5) |
O1 | 0.0482 (10) | 0.0251 (7) | 0.0343 (7) | −0.0044 (7) | −0.0123 (7) | −0.0008 (6) |
C1 | 0.0244 (9) | 0.0224 (9) | 0.0217 (9) | 0.0036 (8) | 0.0018 (7) | 0.0033 (7) |
C5 | 0.0218 (10) | 0.0251 (9) | 0.0229 (9) | 0.0033 (8) | −0.0006 (7) | −0.0012 (7) |
C6 | 0.0223 (9) | 0.0198 (9) | 0.0228 (9) | 0.0028 (7) | 0.0041 (7) | 0.0003 (7) |
C10 | 0.0247 (10) | 0.0187 (9) | 0.0261 (9) | 0.0022 (7) | 0.0050 (7) | −0.0007 (7) |
C2 | 0.0210 (9) | 0.0266 (9) | 0.0253 (9) | −0.0011 (7) | 0.0005 (7) | −0.0016 (7) |
C9 | 0.0300 (10) | 0.0207 (9) | 0.0254 (9) | 0.0012 (8) | 0.0012 (8) | −0.0031 (7) |
C3 | 0.0283 (10) | 0.0210 (9) | 0.0317 (10) | −0.0009 (8) | 0.0079 (8) | 0.0024 (7) |
C7 | 0.0259 (10) | 0.0229 (9) | 0.0233 (9) | 0.0013 (8) | 0.0006 (7) | −0.0022 (7) |
C4 | 0.0287 (10) | 0.0243 (9) | 0.0279 (9) | 0.0043 (8) | 0.0033 (8) | 0.0078 (7) |
C8 | 0.0279 (10) | 0.0236 (9) | 0.0284 (10) | −0.0007 (8) | −0.0022 (8) | 0.0009 (7) |
C15 | 0.0334 (11) | 0.0238 (10) | 0.0346 (10) | −0.0041 (8) | −0.0017 (8) | −0.0011 (8) |
C13 | 0.0355 (12) | 0.0285 (10) | 0.0356 (11) | 0.0057 (9) | 0.0055 (9) | 0.0113 (8) |
C11 | 0.0387 (12) | 0.0205 (9) | 0.0304 (10) | −0.0025 (8) | −0.0007 (9) | 0.0003 (7) |
C14 | 0.0416 (13) | 0.0214 (9) | 0.0455 (12) | −0.0014 (9) | 0.0059 (10) | 0.0050 (8) |
C12 | 0.0438 (13) | 0.0325 (11) | 0.0310 (10) | −0.0018 (10) | −0.0056 (9) | 0.0037 (8) |
F2—C5 | 1.359 (2) | C3—H3 | 0.95 |
F1—C2 | 1.364 (2) | C7—C8 | 1.324 (3) |
O1—C9 | 1.221 (2) | C7—H7 | 0.95 |
C1—C2 | 1.372 (2) | C4—H4 | 0.95 |
C1—C6 | 1.400 (2) | C8—H8 | 0.95 |
C1—H1 | 0.95 | C15—C14 | 1.380 (3) |
C5—C4 | 1.381 (3) | C15—H15 | 0.95 |
C5—C6 | 1.394 (2) | C13—C12 | 1.381 (3) |
C6—C7 | 1.465 (2) | C13—C14 | 1.384 (3) |
C10—C11 | 1.391 (3) | C13—H13 | 0.95 |
C10—C15 | 1.394 (3) | C11—C12 | 1.383 (3) |
C10—C9 | 1.500 (2) | C11—H11 | 0.95 |
C2—C3 | 1.379 (3) | C14—H14 | 0.95 |
C9—C8 | 1.482 (3) | C12—H12 | 0.95 |
C3—C4 | 1.380 (3) | ||
C2—C1—C6 | 119.48 (16) | C6—C7—H7 | 117.1 |
C2—C1—H1 | 120.3 | C3—C4—C5 | 118.97 (16) |
C6—C1—H1 | 120.3 | C3—C4—H4 | 120.5 |
F2—C5—C4 | 117.93 (15) | C5—C4—H4 | 120.5 |
F2—C5—C6 | 118.38 (16) | C7—C8—C9 | 122.22 (18) |
C4—C5—C6 | 123.69 (17) | C7—C8—H8 | 118.9 |
C5—C6—C1 | 116.38 (16) | C9—C8—H8 | 118.9 |
C5—C6—C7 | 121.15 (16) | C14—C15—C10 | 120.66 (18) |
C1—C6—C7 | 122.46 (16) | C14—C15—H15 | 119.7 |
C11—C10—C15 | 118.51 (17) | C10—C15—H15 | 119.7 |
C11—C10—C9 | 123.26 (16) | C12—C13—C14 | 119.74 (18) |
C15—C10—C9 | 118.23 (16) | C12—C13—H13 | 120.1 |
F1—C2—C1 | 118.05 (16) | C14—C13—H13 | 120.1 |
F1—C2—C3 | 118.42 (16) | C12—C11—C10 | 120.75 (18) |
C1—C2—C3 | 123.53 (17) | C12—C11—H11 | 119.6 |
O1—C9—C8 | 120.61 (17) | C10—C11—H11 | 119.6 |
O1—C9—C10 | 120.63 (16) | C15—C14—C13 | 120.22 (18) |
C8—C9—C10 | 118.75 (16) | C15—C14—H14 | 119.9 |
C2—C3—C4 | 117.93 (17) | C13—C14—H14 | 119.9 |
C2—C3—H3 | 121 | C13—C12—C11 | 120.10 (19) |
C4—C3—H3 | 121 | C13—C12—H12 | 120 |
C8—C7—C6 | 125.74 (17) | C11—C12—H12 | 120 |
C8—C7—H7 | 117.1 | ||
F2—C5—C6—C1 | −179.29 (15) | C1—C6—C7—C8 | −6.1 (3) |
C4—C5—C6—C1 | 0.7 (3) | C2—C3—C4—C5 | −0.6 (3) |
F2—C5—C6—C7 | −0.2 (3) | F2—C5—C4—C3 | −179.97 (16) |
C4—C5—C6—C7 | 179.81 (16) | C6—C5—C4—C3 | 0.0 (3) |
C2—C1—C6—C5 | −0.8 (2) | C6—C7—C8—C9 | 177.78 (16) |
C2—C1—C6—C7 | −179.88 (16) | O1—C9—C8—C7 | 9.3 (3) |
C6—C1—C2—F1 | −179.43 (15) | C10—C9—C8—C7 | −169.86 (17) |
C6—C1—C2—C3 | 0.2 (3) | C11—C10—C15—C14 | 0.3 (3) |
C11—C10—C9—O1 | −173.28 (18) | C9—C10—C15—C14 | −178.73 (19) |
C15—C10—C9—O1 | 5.7 (3) | C15—C10—C11—C12 | −1.3 (3) |
C11—C10—C9—C8 | 5.9 (3) | C9—C10—C11—C12 | 177.74 (19) |
C15—C10—C9—C8 | −175.08 (17) | C10—C15—C14—C13 | 0.1 (3) |
F1—C2—C3—C4 | −179.81 (16) | C12—C13—C14—C15 | 0.4 (3) |
C1—C2—C3—C4 | 0.6 (3) | C14—C13—C12—C11 | −1.4 (3) |
C5—C6—C7—C8 | 174.89 (18) | C10—C11—C12—C13 | 1.8 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
C1—H1···F1i | 0.95 | 2.49 | 3.440 (2) | 174 |
C11—H11···F1i | 0.95 | 2.46 | 3.379 (2) | 163 |
Symmetry code: (i) −x+2, −y+1, −z+1. |
Acknowledgements
The authors gratefully acknowledge the financial support and fellowships awarded by the Brazilian funding agencies FAPERJ, CAPES and CNPq. We would also like to thank the LDRX/UFF for the use of X-ray facilities.
References
Bohm, B. A. (1998). In Introduction to Flavonoids. UK: Harwood Academic Publishers. Google Scholar
Bruker (2015). APEX3, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Das, M. & Manna, K. (2016). J. Toxicol. Article ID7651047. Google Scholar
Di Carlos, G., Mascolo, N., Izzo, A. A. & Capasso, F. (1999). Life Sci. 65, 337–353. PubMed Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). J. Appl. Cryst. 41, 466–470. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Sahu, N. K., Balbhadra, S. S., Choudhary, J. & Kohli, D. V. (2012). Curr. Med. Chem. 19, 209–225. Web of Science 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
Singh, P., Anand, A. & Kumar, V. (2014). Eur. J. Med. Chem. 85, 758–777. Web of Science CrossRef CAS PubMed Google Scholar
Sonoda, Y. (2011). Molecules, 16, 119–148. Web of Science CrossRef CAS Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Yadav, V. R., Prasad, S., Sung, B. & Aggarwal, B. B. (2011). Int. Immunopharmacol. 11, 295–309. Web of Science CrossRef CAS PubMed Google Scholar
Yazdan, S. K., Sagar, D. V. & Shaik, A. B. (2015). Org. Med. Chem. Int. J. 1, 1–9. Google Scholar
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