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Logo of actae2this articlesearchopen accesssubmitActa Crystallographica Section E: Crystallographic CommunicationsActa Crystallographica Section E: Crystallographic Communications
 
Acta Crystallogr E Crystallogr Commun. 2016 May 1; 72(Pt 5): 648–651.
Published online 2016 April 8. doi:  10.1107/S2056989016005028
PMCID: PMC4908534

(E)-1-(Anthracen-9-yl)-3-(2-chloro-6-fluoro­phen­yl)prop-2-en-1-one: crystal structure and Hirshfeld surface analysis

Abstract

In the title compound, C23H14ClFO, the enone moiety adopts an E conformation. The dihedral angle between the benzene and anthracene ring is 63.42 (8)° and an intra­molecular C—H(...)F hydrogen bond generates an S(6) ring motif. In the crystal, mol­ecules are arranged into centrosymmetric dimers via pairs of C—H(...)F hydrogen bonds. The crystal structure also features C—H(...)π and π–π inter­actions. Hirshfeld surface analysis was used to confirm the existence of inter­molecular inter­actions.

Keywords: crystal structure, chalcone, hydrogen bonding, Hirshfeld surface analysis

Chemical context  

The biological properties of chalcone derivatives such as anti­cancer (Bhat et al., 2005  ), anti­malarial (Xue et al., 2004  ), anti-oxidant and anti­microbial (Yayli et al., 2006  ), anti­platelet (Zhao et al., 2005  ) as well as anti-inflammatory (Madan et al., 2000  ) have been studied extensively and developed. As part of our own studies in this area, we hereby report the synthesis and crystal structure of the title compound.

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Object name is e-72-00648-scheme1.jpg

Structural commentary  

The mol­ecular structure of the title chalcone is shown in Fig. 1  . The enone moiety (O1/C7–C9) adopts an E conformation with respect to the C7=C8 bond. The anthracene ring system (C10–C23) is twisted at the C9–C10 bond from the (E)-3-(2-chloro-6-fluoro­phen­yl)acryl­aldehyde moiety [maximum deviation = 0.193 (16) Å for atom O1] with a C8—C9—C10—C23 torsion angle of −61.4 (2)°. The terminal benzene and anthracene ring systems (C1–C6 and C10–C23, respectively) form a dihedral angle of 63.42 (8)°. The least-squares plane through the enone moiety [O1/C7–C9) with a maximum deviation of 0.033 (2) Å for atom C9] makes dihedral angles of 5.62 (13) and 59.18 (12)° with the benzene (C1–C6) and anthracene (C10–C23) rings, respectively. An intra­molecular C8—H8A(...)F1 hydrogen bond is observed, generating an S(6) ring motif. The bond lengths and angles are comparable with those in previously reported structures (Razak et al., 2009  ; Ngaini et al., 2011  ).

Figure 1
The mol­ecular structure of the title compound, showing 50% probability displacement ellipsoids. The intra­molecular C—H(...)F hydrogen bond is shown as a dashed line.

Supra­molecular features  

In the crystal (Fig. 2  ), the mol­ecules are arranged into centrosymmetric dimers via pairs of C17—H17A(...)F1 (Table 1  ) hydrogen bonds. The crystal structure also features C14—H14A(...)Cg1 (Fig. 3  ) and Cg1(...)Cg1(1 − x, −y, 1 − z) inter­actions [centroid-to-centroid distance = 3.7557 (13) Å; Cg1 is the centroid of the C1–C6 ring].

Figure 2
The crystal packing showing the mol­ecules arranged into centrosymmetric dimers. The H atoms not involved in the inter­molecular inter­actions (dashed lines) have been omitted for clarity.
Figure 3
Detail of the crystal structure showing the C14—H14A(...)Cg1 inter­action where Cg1 is the centroid of C1–C6 ring.
Table 1
Hydrogen-bond geometry (Å, °)

Hirshfeld surfaces analysis  

The inter­molecular inter­actions of the title compound can be visualized using Hirshfeld surface analysis (Wolff et al., 2012  ). The Hirshfeld surfaces mapped over d norm are shown in Fig. 4  . The 2-D fingerprint plots showing the occurrence of different kinds of inter­molecular contacts are shown in Fig. 5  .

Figure 4
d norm mapped on the Hirshfeld surface for visualizing the inter­molecular inter­actions of the title chalcone compound. Dotted lines (green) represent hydrogen bonds.
Figure 5
The 2-Dimensional fingerprint plot for the title chalcone compound showing contributions from different contacts.

The C17—H17A(...)F1 inter­actions are shown on the Hirshfeld surfaces marked with a bright-red spot for short contacts·The H(...)F/F(...)H contacts comprise 6.3% of the total Hirshfeld surface, represented by two symmetrical narrow pointed spikes with de + di ~2.3 Å, suggesting the presence of a non-classical C—H(...)F hydrogen bond. The H(...)H contacts are shown on the fingerprint plot as one distinct spike with the minimum value of de + di. These contacts represent the largest contribution within the Hirshfeld surfaces (38.8%).

Significant C—H(...)π inter­actions (22.8%) can be also be seen, indicated by the wings of de + di ~2.6 Å on the fingerprint plot. The presence of π–π inter­actions is shown as C(...)C contacts, which contribute 8.9% of the Hirshfeld surfaces. The presence of these inter­actions can also be shown by the Hirshfeld surfaces mapped by shape index (Fig. 6  ) and the Hirshfeld surfaces mapped with curvedness (Fig. 7  ).

Figure 6
Hirshfeld surface mapped over the shape index of the chalcone compound in (a) front view and (b) back view.
Figure 7
Hirshfeld surface mapped over curvedness of the chalcone compound in (a) front view and (b) back view.

Synthesis and crystallization  

A mixture of 9-acetyl­anthracene (0.1 mol, 0.11 g) and 2-chloro-6-fluoro­benzaldehyde (0.1 mol, 0.08 g) was dissolved in methanol (20 ml). A catalytic amount of NaOH (5 ml, 20%) was added to the solution dropwise with vigorous stirring. The reaction mixture was stirred for about 5–6 h at room temperature. After stirring, the contents of the flask were poured into ice-cold water (50 ml) and the resulting crude solid was collected by filtration. The compound was dried and purified by repeated recrystallization from acetone solution, forming yellow plates.

Refinement details  

Crystal data collection and structure refinement details are summarized in Table 2  . All H atoms were positioned geometrically (C—H = 0.93 Å) and refined using a riding model with U iso(H) = 1.2U eq(C). The most disagreeable reflections (−1 − 2 4 and −1 1 0) were omitted from the final refinement.

Table 2
Experimental details

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989016005028/hb7569sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989016005028/hb7569Isup2.hkl

CCDC reference: 1470351

Additional supporting information: crystallographic information; 3D view; checkCIF report

Acknowledgments

The authors thank the Malaysian Government and Universiti Sains Malaysia (USM) for the research facilities and Research University Grant No.1001/PFIZIK/811238 to conduct this work. NCK thanks the Malaysian Government for a MyBrain15 (MyPhD) scholarship

supplementary crystallographic information

Crystal data

C23H14ClFOZ = 2
Mr = 360.79F(000) = 372
Triclinic, P1Dx = 1.383 Mg m3
a = 9.2846 (9) ÅMo Kα radiation, λ = 0.71073 Å
b = 9.8777 (10) ÅCell parameters from 4550 reflections
c = 10.3624 (11) Åθ = 2.5–29.4°
α = 94.364 (2)°µ = 0.24 mm1
β = 113.3517 (19)°T = 296 K
γ = 92.866 (2)°Plate, yellow
V = 866.63 (15) Å30.43 × 0.39 × 0.11 mm

Data collection

Bruker SMART APEXII DUO CCD diffractometer2973 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.027
[var phi] and ω scansθmax = 27.5°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2009)h = −12→12
Tmin = 0.905, Tmax = 0.974k = −12→12
15408 measured reflectionsl = −13→13
3917 independent reflections

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)] = 0.046Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.159H atoms treated by a mixture of independent and constrained refinement
S = 1.04w = 1/[σ2(Fo2) + (0.0894P)2 + 0.1829P] where P = (Fo2 + 2Fc2)/3
3917 reflections(Δ/σ)max = 0.001
235 parametersΔρmax = 0.27 e Å3
0 restraintsΔρmin = −0.38 e Å3

Special details

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.
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > 2sigma(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

xyzUiso*/Ueq
F10.34800 (14)0.90969 (12)0.72673 (15)0.0699 (4)
Cl10.88071 (6)0.82117 (5)1.09430 (6)0.0677 (2)
O10.52128 (16)0.43191 (13)0.84772 (16)0.0550 (4)
C10.4948 (2)0.95649 (18)0.8188 (2)0.0458 (4)
C20.5336 (3)1.09407 (19)0.8323 (2)0.0550 (5)
H2A0.46081.15170.78070.066*
C30.6821 (3)1.14449 (19)0.9237 (2)0.0570 (5)
H3A0.71161.23720.93270.068*
C40.7881 (2)1.05996 (19)1.0024 (2)0.0526 (5)
H4A0.88861.09501.06480.063*
C50.7438 (2)0.92195 (17)0.98776 (19)0.0429 (4)
C60.5955 (2)0.86314 (16)0.89285 (17)0.0380 (4)
C70.5552 (2)0.71650 (16)0.87498 (19)0.0404 (4)
H7A0.63080.66700.93640.048*
C80.4263 (2)0.64341 (17)0.7838 (2)0.0434 (4)
H8A0.34450.68710.72170.052*
C90.4112 (2)0.49374 (17)0.77988 (19)0.0398 (4)
C100.2559 (2)0.41801 (16)0.68598 (18)0.0382 (4)
C110.2509 (2)0.31627 (17)0.58084 (18)0.0417 (4)
C120.3822 (3)0.2912 (2)0.5479 (2)0.0565 (5)
H12A0.47630.34560.59470.068*
C130.3721 (3)0.1887 (3)0.4489 (3)0.0718 (7)
H13A0.46000.17360.42950.086*
C140.2325 (4)0.1053 (3)0.3755 (3)0.0800 (8)
H14A0.22910.03440.30960.096*
C150.1029 (3)0.1272 (3)0.3997 (2)0.0700 (6)
H15A0.01030.07180.34960.084*
C160.1060 (2)0.23471 (19)0.50155 (19)0.0496 (4)
C17−0.0258 (2)0.2597 (2)0.5264 (2)0.0551 (5)
H17A−0.11910.20550.47480.066*
C18−0.0244 (2)0.3629 (2)0.6260 (2)0.0479 (4)
C19−0.1599 (2)0.3878 (3)0.6524 (3)0.0683 (6)
H19A−0.25460.33640.59860.082*
C20−0.1546 (3)0.4844 (3)0.7537 (3)0.0756 (7)
H20A−0.24550.50040.76770.091*
C21−0.0121 (3)0.5609 (2)0.8381 (3)0.0679 (6)
H21A−0.00920.62630.90870.081*
C220.1212 (2)0.5408 (2)0.8184 (2)0.0528 (5)
H22A0.21470.59160.87690.063*
C230.1206 (2)0.44299 (16)0.70929 (18)0.0397 (4)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
F10.0491 (7)0.0501 (7)0.0787 (9)0.0030 (5)−0.0066 (6)0.0012 (6)
Cl10.0519 (3)0.0535 (3)0.0713 (4)−0.0034 (2)−0.0026 (3)0.0099 (2)
O10.0412 (7)0.0393 (7)0.0702 (9)0.0012 (5)0.0087 (6)−0.0007 (6)
C10.0465 (10)0.0396 (9)0.0443 (9)0.0005 (7)0.0124 (8)−0.0026 (7)
C20.0695 (13)0.0368 (9)0.0554 (11)0.0083 (9)0.0216 (10)0.0036 (8)
C30.0770 (14)0.0323 (9)0.0588 (12)−0.0059 (9)0.0269 (11)−0.0033 (8)
C40.0562 (11)0.0411 (9)0.0514 (11)−0.0150 (8)0.0166 (9)−0.0070 (8)
C50.0447 (9)0.0392 (8)0.0405 (9)−0.0053 (7)0.0145 (7)−0.0009 (7)
C60.0423 (9)0.0335 (8)0.0377 (8)−0.0024 (6)0.0170 (7)−0.0011 (6)
C70.0403 (9)0.0334 (8)0.0452 (9)−0.0010 (7)0.0161 (7)0.0006 (7)
C80.0388 (9)0.0353 (8)0.0504 (10)−0.0022 (7)0.0128 (8)0.0026 (7)
C90.0368 (8)0.0360 (8)0.0455 (9)−0.0032 (7)0.0173 (7)−0.0026 (7)
C100.0376 (8)0.0336 (8)0.0403 (8)−0.0034 (6)0.0137 (7)0.0011 (6)
C110.0439 (9)0.0408 (9)0.0368 (8)−0.0021 (7)0.0136 (7)0.0007 (7)
C120.0575 (12)0.0626 (12)0.0523 (11)−0.0026 (10)0.0281 (10)−0.0063 (9)
C130.0805 (17)0.0812 (16)0.0618 (14)0.0067 (13)0.0405 (13)−0.0115 (12)
C140.101 (2)0.0781 (16)0.0578 (14)−0.0017 (15)0.0358 (14)−0.0256 (12)
C150.0773 (15)0.0670 (14)0.0508 (12)−0.0131 (12)0.0171 (11)−0.0213 (10)
C160.0523 (11)0.0490 (10)0.0376 (9)−0.0053 (8)0.0102 (8)−0.0034 (7)
C170.0403 (10)0.0614 (12)0.0475 (10)−0.0108 (8)0.0043 (8)−0.0053 (9)
C180.0357 (9)0.0537 (10)0.0470 (10)−0.0008 (7)0.0096 (8)0.0051 (8)
C190.0352 (10)0.0876 (16)0.0737 (15)−0.0047 (10)0.0160 (10)−0.0008 (13)
C200.0488 (12)0.0917 (18)0.0939 (19)0.0084 (12)0.0379 (13)0.0001 (15)
C210.0670 (14)0.0652 (13)0.0828 (16)0.0050 (11)0.0444 (13)−0.0055 (12)
C220.0486 (10)0.0475 (10)0.0636 (12)−0.0039 (8)0.0273 (9)−0.0080 (9)
C230.0383 (8)0.0362 (8)0.0422 (9)−0.0005 (7)0.0140 (7)0.0040 (7)

Geometric parameters (Å, º)

F1—C11.350 (2)C12—C131.358 (3)
Cl1—C51.734 (2)C12—H12A0.9300
O1—C91.212 (2)C13—C141.398 (4)
C1—C21.371 (3)C13—H13A0.9300
C1—C61.392 (3)C14—C151.347 (4)
C2—C31.367 (3)C14—H14A0.9300
C2—H2A0.9300C15—C161.430 (3)
C3—C41.371 (3)C15—H15A0.9300
C3—H3A0.9300C16—C171.377 (3)
C4—C51.383 (2)C17—C181.391 (3)
C4—H4A0.9300C17—H17A0.9300
C5—C61.400 (2)C18—C191.419 (3)
C6—C71.457 (2)C18—C231.432 (2)
C7—C81.326 (2)C19—C201.348 (4)
C7—H7A0.9300C19—H19A0.9300
C8—C91.474 (2)C20—C211.403 (4)
C8—H8A0.9300C20—H20A0.9300
C9—C101.501 (2)C21—C221.353 (3)
C10—C231.401 (2)C21—H21A0.9300
C10—C111.410 (2)C22—C231.429 (3)
C11—C121.418 (3)C22—H22A0.9300
C11—C161.431 (2)
F1—C1—C2116.89 (17)C11—C12—H12A119.6
F1—C1—C6118.40 (15)C12—C13—C14121.4 (2)
C2—C1—C6124.72 (18)C12—C13—H13A119.3
C3—C2—C1118.30 (19)C14—C13—H13A119.3
C3—C2—H2A120.9C15—C14—C13120.3 (2)
C1—C2—H2A120.9C15—C14—H14A119.9
C2—C3—C4120.80 (17)C13—C14—H14A119.9
C2—C3—H3A119.6C14—C15—C16120.8 (2)
C4—C3—H3A119.6C14—C15—H15A119.6
C3—C4—C5119.26 (18)C16—C15—H15A119.6
C3—C4—H4A120.4C17—C16—C15121.58 (19)
C5—C4—H4A120.4C17—C16—C11119.60 (17)
C4—C5—C6122.82 (17)C15—C16—C11118.81 (19)
C4—C5—Cl1117.09 (14)C16—C17—C18122.30 (17)
C6—C5—Cl1120.08 (13)C16—C17—H17A118.8
C1—C6—C5114.05 (15)C18—C17—H17A118.8
C1—C6—C7124.47 (16)C17—C18—C19122.26 (18)
C5—C6—C7121.48 (16)C17—C18—C23118.89 (17)
C8—C7—C6129.39 (17)C19—C18—C23118.79 (18)
C8—C7—H7A115.3C20—C19—C18121.4 (2)
C6—C7—H7A115.3C20—C19—H19A119.3
C7—C8—C9120.76 (17)C18—C19—H19A119.3
C7—C8—H8A119.6C19—C20—C21120.1 (2)
C9—C8—H8A119.6C19—C20—H20A120.0
O1—C9—C8121.54 (15)C21—C20—H20A120.0
O1—C9—C10120.20 (15)C22—C21—C20121.0 (2)
C8—C9—C10118.24 (15)C22—C21—H21A119.5
C23—C10—C11120.91 (15)C20—C21—H21A119.5
C23—C10—C9119.90 (14)C21—C22—C23121.0 (2)
C11—C10—C9119.07 (15)C21—C22—H22A119.5
C10—C11—C12123.31 (16)C23—C22—H22A119.5
C10—C11—C16118.82 (16)C10—C23—C22122.97 (16)
C12—C11—C16117.86 (16)C10—C23—C18119.40 (16)
C13—C12—C11120.8 (2)C22—C23—C18117.55 (16)
C13—C12—H12A119.6
F1—C1—C2—C3−179.33 (18)C11—C12—C13—C140.5 (4)
C6—C1—C2—C30.7 (3)C12—C13—C14—C151.5 (4)
C1—C2—C3—C4−1.6 (3)C13—C14—C15—C16−0.7 (4)
C2—C3—C4—C50.5 (3)C14—C15—C16—C17179.2 (2)
C3—C4—C5—C61.7 (3)C14—C15—C16—C11−1.9 (4)
C3—C4—C5—Cl1−177.92 (16)C10—C11—C16—C171.9 (3)
F1—C1—C6—C5−178.72 (16)C12—C11—C16—C17−177.37 (19)
C2—C1—C6—C51.2 (3)C10—C11—C16—C15−177.00 (19)
F1—C1—C6—C71.9 (3)C12—C11—C16—C153.7 (3)
C2—C1—C6—C7−178.11 (18)C15—C16—C17—C18179.4 (2)
C4—C5—C6—C1−2.4 (2)C11—C16—C17—C180.5 (3)
Cl1—C5—C6—C1177.15 (13)C16—C17—C18—C19−179.5 (2)
C4—C5—C6—C7176.95 (17)C16—C17—C18—C23−2.3 (3)
Cl1—C5—C6—C7−3.5 (2)C17—C18—C19—C20177.0 (2)
C1—C6—C7—C84.7 (3)C23—C18—C19—C20−0.1 (4)
C5—C6—C7—C8−174.62 (18)C18—C19—C20—C21−1.5 (4)
C6—C7—C8—C9177.73 (16)C19—C20—C21—C221.0 (4)
C7—C8—C9—O1−8.3 (3)C20—C21—C22—C231.2 (4)
C7—C8—C9—C10173.29 (16)C11—C10—C23—C22177.24 (17)
O1—C9—C10—C23120.22 (19)C9—C10—C23—C221.3 (3)
C8—C9—C10—C23−61.4 (2)C11—C10—C23—C180.7 (3)
O1—C9—C10—C11−55.8 (2)C9—C10—C23—C18−175.30 (15)
C8—C9—C10—C11122.59 (18)C21—C22—C23—C10−179.4 (2)
C23—C10—C11—C12176.76 (17)C21—C22—C23—C18−2.8 (3)
C9—C10—C11—C12−7.2 (3)C17—C18—C23—C101.7 (3)
C23—C10—C11—C16−2.5 (3)C19—C18—C23—C10178.96 (19)
C9—C10—C11—C16173.54 (16)C17—C18—C23—C22−175.05 (19)
C10—C11—C12—C13177.7 (2)C19—C18—C23—C222.2 (3)
C16—C11—C12—C13−3.0 (3)

Hydrogen-bond geometry (Å, º)

Cg1 is the centroid of the C1–C6 ring.

D—H···AD—HH···AD···AD—H···A
C8—H8A···F10.932.192.808 (2)123
C17—H17A···F1i0.932.463.353 (2)161
C14—H14A···Cg1ii0.932.993.712 (3)136

Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x+1, −y+1, −z+1.

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Articles from Acta Crystallographica Section E: Crystallographic Communications are provided here courtesy of International Union of Crystallography