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Acta Crystallogr Sect E Struct Rep Online. 2012 May 1; 68(Pt 5): o1413.
Published online 2012 April 18. doi:  10.1107/S1600536812015589
PMCID: PMC3344538

4-[(1E)-3-(2,6-Dichloro-3-fluoro­phen­yl)-3-oxoprop-1-en-1-yl]benzonitrile

Abstract

In the title mol­ecule, C16H8Cl2FNO, the benzene rings form a dihedral angle of 78.69 (8)°. The F atom is disordered over two positions in a 0.530 (3):0.470 (3) ratio. The crystal packing exhibits π–π inter­actions between dichloro-substituted rings [centroid–centroid distance = 3.6671 (10) Å] and weak inter­molecular C—H(...)F contacts.

Related literature  

For the biological activity of chalcones, see: Rajendra Prasad et al. (2008 [triangle]); Shivakumar et al. (2005 [triangle]); Churkin et al. (1982 [triangle]); Herencia et al. (1998 [triangle]). For a related structure, see: Betz et al. (2012 [triangle]). For the graph-set analysis of hydrogen bonds, see: Etter et al. (1990 [triangle]); Bernstein et al. (1995 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-68-o1413-scheme1.jpg

Experimental  

Crystal data  

  • C16H8Cl2FNO
  • M r = 320.13
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-68-o1413-efi1.jpg
  • a = 13.2751 (3) Å
  • b = 8.5002 (2) Å
  • c = 13.9854 (3) Å
  • β = 116.773 (1)°
  • V = 1408.95 (6) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.47 mm−1
  • T = 200 K
  • 0.55 × 0.32 × 0.20 mm

Data collection  

  • Bruker APEXII CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2008 [triangle]) T min = 0.783, T max = 0.913
  • 12885 measured reflections
  • 3480 independent reflections
  • 2904 reflections with I > 2σ(I)
  • R int = 0.013

Refinement  

  • R[F 2 > 2σ(F 2)] = 0.037
  • wR(F 2) = 0.098
  • S = 1.05
  • 3480 reflections
  • 200 parameters
  • H-atom parameters constrained
  • Δρmax = 0.41 e Å−3
  • Δρmin = −0.43 e Å−3

Data collection: APEX2 (Bruker, 2010 [triangle]); cell refinement: SAINT (Bruker, 2010 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: ORTEP-3 (Farrugia, 1997 [triangle]) and Mercury (Macrae et al., 2008 [triangle]); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812015589/cv5282sup1.cif

Supplementary material file. DOI: 10.1107/S1600536812015589/cv5282Isup2.cdx

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812015589/cv5282Isup3.hkl

Supplementary material file. DOI: 10.1107/S1600536812015589/cv5282Isup4.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

ASP thanks the University of Mysore for the research facilities.

supplementary crystallographic information

Comment

Chalcones are the products of condensation reactions of aromatic aldehydes with acetophenones in the presence of alkali. Chalcones constitute an important group of natural products, and some of them possess a wide range of biological activities such as antimicrobial (Rajendra Prasad et al., 2008), antitubercular (Shivakumar et al., 2005), antiviral (Churkin et al., 1982) and anti-inflammatory activity (Herencia et al., 1998). The crystal structures of some chalcones such as have been reported in the literature. As a part of our ongoing studies on chalcones, the title compound (I) has been synthesized and characterized by X-ray diffraction.

In (I) (Fig. 1), all bond lengths and angles are normal and correspond to those observed in (2E)-1-(2,6-dichloro-3-fluorophenyl)-3-(4-fluorophenyl)prop-2-en-1-one (Betz et al., 2012). The fluorine atom is disordered over two positions with site occupancy factors of 0.530 (3) and 0.470 (3), respectively. The mean planes of the two aromatic rings for a dihedral angle of 78.69 (8)°.

In the crystal, C–H···F contacts (Table 1) whose range falls by more than 0.1 Å below the sum of van-der-Waals radii of the respective atoms are present. These are supported by one of the vinylic hydrogen atoms as well as the disordered fluorine atom. In terms of graph-set analysis (Etter et al., 1990; Bernstein et al., 1995), the descriptor for these hydrogen bonds is C11(8) on the unary level. The shortest intercentroid distance between two aromatic systems was found at 3.6674 (10) Å and is apparent between the halogenated phenyl rings. The packing of the title compound in the crystal structure is shown in Figure 2.

Experimental

To a stirred solution of 1-(2,6-dichloro-3-fluorophenyl)ethanone (1 g, 4.8 mmol) and 4-formylbenzonitrile (0.62 g, 4.8 mmol) in ethanol (10 ml), powdered KOH (0.40 g, 7.2 mmol) was added at 273 K. The reaction mixture was stirred at room temperature for 2 h. After completion of the reaction, the mixture was poured into ice cold water and subsequently acidified with 1.5 N HCl (pH ~3). The precipitated solid was filtered and dried to afford 1 g of the title compound as pale yellow solid in 91% yield. The single-crystal was grown from a mixture of toluene:acetone (v:v = 1:1) by slow evaporation at room temperature (m.p.: 414–417 K).

Refinement

C-bound H atoms were placed in calculated positions (C—H 0.95 Å) and were included in the refinement in the riding model approximation, with U(H) set to 1.2Ueq(C).

Figures

Fig. 1.
The molecular structure of the title compound showing the atomic numbering and 50% probability displacement ellipsoids. Only the major part of the disordered fluorine atom is shown.
Fig. 2.
A portion of the crystal packing viewed along [010].

Crystal data

C16H8Cl2FNOF(000) = 648
Mr = 320.13Dx = 1.509 Mg m3
Monoclinic, P21/cMelting point = 414–417 K
Hall symbol: -P 2ybcMo Kα radiation, λ = 0.71073 Å
a = 13.2751 (3) ÅCell parameters from 7660 reflections
b = 8.5002 (2) Åθ = 2.9–28.3°
c = 13.9854 (3) ŵ = 0.47 mm1
β = 116.773 (1)°T = 200 K
V = 1408.95 (6) Å3Platelet, green
Z = 40.55 × 0.32 × 0.20 mm

Data collection

Bruker APEXII CCD diffractometer3480 independent reflections
Radiation source: fine-focus sealed tube2904 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.013
[var phi] and ω scansθmax = 28.3°, θmin = 2.9°
Absorption correction: multi-scan (SADABS; Bruker, 2008)h = −17→17
Tmin = 0.783, Tmax = 0.913k = −8→11
12885 measured reflectionsl = −18→18

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.037Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.098H-atom parameters constrained
S = 1.05w = 1/[σ2(Fo2) + (0.0358P)2 + 0.6287P] where P = (Fo2 + 2Fc2)/3
3480 reflections(Δ/σ)max < 0.001
200 parametersΔρmax = 0.41 e Å3
0 restraintsΔρmin = −0.43 e Å3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

xyzUiso*/UeqOcc. (<1)
Cl10.32198 (4)0.25664 (5)0.03764 (4)0.05826 (14)
Cl20.43426 (5)0.87196 (6)0.08058 (4)0.06998 (17)
O10.23229 (11)0.62352 (16)−0.09939 (9)0.0582 (3)
N1−0.11644 (13)0.5937 (3)0.40221 (14)0.0785 (6)
C10.21695 (12)0.57997 (17)0.14653 (12)0.0392 (3)
H10.29270.54730.18910.047*
C20.18838 (14)0.6169 (2)0.04481 (13)0.0460 (4)
H20.11400.65440.00170.055*
C30.26474 (14)0.60326 (19)−0.00432 (12)0.0435 (3)
C4−0.06074 (13)0.5902 (2)0.35969 (14)0.0525 (4)
C110.14352 (12)0.58457 (17)0.19935 (11)0.0370 (3)
C120.03215 (13)0.6397 (2)0.14813 (13)0.0487 (4)
H120.00220.67710.07650.058*
C13−0.03410 (13)0.6403 (2)0.20037 (13)0.0489 (4)
H13−0.10970.67710.16470.059*
C140.00933 (12)0.58722 (18)0.30543 (12)0.0408 (3)
C150.11978 (12)0.5340 (2)0.35809 (12)0.0440 (3)
H150.14980.49840.43010.053*
C160.18571 (12)0.53320 (19)0.30467 (12)0.0407 (3)
H160.26140.49680.34070.049*
C210.38739 (13)0.56076 (18)0.06658 (11)0.0394 (3)
C220.42114 (12)0.40474 (19)0.08897 (11)0.0404 (3)
C240.61343 (14)0.4808 (3)0.19589 (13)0.0538 (4)
H240.68990.45390.24090.065*
C260.47029 (15)0.6754 (2)0.10883 (13)0.0467 (4)
C230.53293 (14)0.3657 (2)0.15222 (13)0.0474 (4)
H230.55420.25820.16560.057*0.470 (3)
F1B0.6550 (2)0.7502 (4)0.2076 (2)0.0847 (11)0.470 (3)
C250.58158 (15)0.6354 (2)0.17347 (14)0.0545 (4)
H250.63670.71600.20270.065*0.530 (3)
F1A0.56085 (16)0.2148 (3)0.16948 (16)0.0610 (7)0.530 (3)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Cl10.0520 (2)0.0417 (2)0.0616 (3)−0.00337 (17)0.00832 (19)0.00136 (18)
Cl20.1033 (4)0.0436 (2)0.0648 (3)−0.0126 (2)0.0394 (3)−0.0003 (2)
O10.0635 (7)0.0718 (9)0.0403 (6)0.0168 (6)0.0242 (6)0.0145 (6)
N10.0455 (8)0.1321 (18)0.0629 (10)0.0129 (10)0.0288 (8)−0.0008 (11)
C10.0376 (7)0.0386 (7)0.0407 (7)0.0002 (6)0.0171 (6)0.0005 (6)
C20.0444 (8)0.0502 (9)0.0432 (8)0.0089 (7)0.0195 (7)0.0076 (7)
C30.0508 (8)0.0405 (8)0.0406 (8)0.0047 (7)0.0217 (7)0.0052 (6)
C40.0361 (7)0.0725 (12)0.0473 (9)0.0051 (8)0.0172 (7)−0.0027 (8)
C110.0355 (7)0.0349 (7)0.0389 (7)−0.0007 (6)0.0153 (6)−0.0010 (6)
C120.0397 (8)0.0596 (10)0.0418 (8)0.0076 (7)0.0139 (6)0.0099 (7)
C130.0336 (7)0.0586 (10)0.0497 (9)0.0088 (7)0.0146 (6)0.0058 (7)
C140.0346 (7)0.0428 (8)0.0451 (8)−0.0006 (6)0.0182 (6)−0.0052 (6)
C150.0392 (7)0.0525 (9)0.0404 (7)0.0054 (6)0.0179 (6)0.0025 (7)
C160.0332 (7)0.0465 (8)0.0401 (7)0.0059 (6)0.0147 (6)0.0024 (6)
C210.0461 (8)0.0440 (8)0.0327 (7)0.0000 (6)0.0219 (6)0.0015 (6)
C220.0405 (7)0.0443 (8)0.0348 (7)−0.0011 (6)0.0155 (6)−0.0012 (6)
C240.0390 (8)0.0831 (13)0.0393 (8)−0.0030 (8)0.0176 (7)−0.0014 (8)
C260.0603 (9)0.0472 (9)0.0411 (8)−0.0065 (7)0.0303 (7)−0.0005 (7)
C230.0464 (8)0.0571 (10)0.0389 (7)0.0080 (7)0.0193 (7)0.0015 (7)
F1B0.0738 (17)0.107 (2)0.0622 (16)−0.0519 (16)0.0211 (13)−0.0060 (14)
C250.0535 (9)0.0717 (12)0.0433 (8)−0.0211 (9)0.0260 (8)−0.0071 (8)
F1A0.0529 (11)0.0588 (13)0.0594 (12)0.0184 (9)0.0147 (9)0.0096 (9)

Geometric parameters (Å, º)

Cl1—C221.7267 (16)C13—H130.9500
Cl2—C261.7338 (18)C14—C151.387 (2)
O1—C31.2112 (18)C15—C161.383 (2)
N1—C41.139 (2)C15—H150.9500
C1—C21.334 (2)C16—H160.9500
C1—C111.465 (2)C21—C261.387 (2)
C1—H10.9500C21—C221.390 (2)
C2—C31.463 (2)C22—C231.383 (2)
C2—H20.9500C24—C231.373 (3)
C3—C211.520 (2)C24—C251.373 (3)
C4—C141.441 (2)C24—H240.9500
C11—C161.390 (2)C26—C251.383 (3)
C11—C121.402 (2)C23—F1A1.327 (3)
C12—C131.373 (2)C23—H230.9500
C12—H120.9500F1B—C251.308 (3)
C13—C141.390 (2)C25—H250.9500
C2—C1—C11126.67 (14)C15—C16—H16119.3
C2—C1—H1116.7C11—C16—H16119.3
C11—C1—H1116.7C26—C21—C22117.46 (14)
C1—C2—C3123.90 (14)C26—C21—C3121.47 (15)
C1—C2—H2118.1C22—C21—C3121.05 (14)
C3—C2—H2118.1C23—C22—C21121.15 (15)
O1—C3—C2121.68 (15)C23—C22—Cl1119.24 (13)
O1—C3—C21119.79 (14)C21—C22—Cl1119.61 (11)
C2—C3—C21118.53 (13)C23—C24—C25118.87 (16)
N1—C4—C14179.4 (2)C23—C24—H24120.6
C16—C11—C12118.39 (14)C25—C24—H24120.6
C16—C11—C1118.96 (13)C25—C26—C21120.98 (17)
C12—C11—C1122.65 (13)C25—C26—Cl2119.32 (14)
C13—C12—C11120.68 (15)C21—C26—Cl2119.70 (13)
C13—C12—H12119.7F1A—C23—C24120.69 (17)
C11—C12—H12119.7F1A—C23—C22118.67 (17)
C12—C13—C14120.06 (14)C24—C23—C22120.64 (17)
C12—C13—H13120.0F1A—C23—H231.0
C14—C13—H13120.0C24—C23—H23119.7
C15—C14—C13120.21 (14)C22—C23—H23119.7
C15—C14—C4120.30 (14)F1B—C25—C24121.9 (2)
C13—C14—C4119.48 (14)F1B—C25—C26117.1 (2)
C16—C15—C14119.30 (14)C24—C25—C26120.87 (16)
C16—C15—H15120.4F1B—C25—H253.7
C14—C15—H15120.4C24—C25—H25119.6
C15—C16—C11121.34 (13)C26—C25—H25119.6
C11—C1—C2—C3−177.25 (15)C26—C21—C22—C230.9 (2)
C1—C2—C3—O1172.76 (17)C3—C21—C22—C23179.07 (13)
C1—C2—C3—C21−6.6 (2)C26—C21—C22—Cl1−179.43 (11)
C2—C1—C11—C16176.31 (16)C3—C21—C22—Cl1−1.24 (19)
C2—C1—C11—C12−4.1 (3)C22—C21—C26—C25−2.0 (2)
C16—C11—C12—C13−1.1 (2)C3—C21—C26—C25179.84 (14)
C1—C11—C12—C13179.29 (16)C22—C21—C26—Cl2178.12 (11)
C11—C12—C13—C140.6 (3)C3—C21—C26—Cl2−0.07 (19)
C12—C13—C14—C150.2 (3)C25—C24—C23—F1A178.08 (18)
C12—C13—C14—C4179.32 (17)C25—C24—C23—C22−1.7 (2)
N1—C4—C14—C15136 (21)C21—C22—C23—F1A−178.81 (16)
N1—C4—C14—C13−43 (21)Cl1—C22—C23—F1A1.5 (2)
C13—C14—C15—C16−0.5 (2)C21—C22—C23—C240.9 (2)
C4—C14—C15—C16−179.57 (16)Cl1—C22—C23—C24−178.75 (12)
C14—C15—C16—C110.0 (2)C23—C24—C25—F1B−176.2 (2)
C12—C11—C16—C150.8 (2)C23—C24—C25—C260.6 (2)
C1—C11—C16—C15−179.54 (14)C21—C26—C25—F1B178.18 (19)
O1—C3—C21—C2684.6 (2)Cl2—C26—C25—F1B−1.9 (2)
C2—C3—C21—C26−96.08 (18)C21—C26—C25—C241.3 (2)
O1—C3—C21—C22−93.55 (19)Cl2—C26—C25—C24−178.81 (13)
C2—C3—C21—C2285.81 (19)

Hydrogen-bond geometry (Å, º)

D—H···AD—HH···AD···AD—H···A
C1—H1···F1Ai0.952.503.130 (2)124

Symmetry code: (i) −x+1, y+1/2, −z+1/2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: CV5282).

References

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