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Acta Cryst. (2009). E65, o1472-o1473    [ doi:10.1107/S1600536809020145 ]

(E)-3-(2,6-Dichlorophenyl)-1-(4-methoxyphenyl)prop-2-en-1-one

L. Benmekhbi, R. Belhouas, S. Bouacida, S. Mosbah and L. Bencharif

Abstract top

In the title compound, C16H12Cl2O2, the dichlorophenyl and methoxyphenyl groups are linked by a prop-2-en-1-one group. The C=C double bond is trans configured. The molecule is not planar, as can be seen from the dihedral angle of 6.21 (7)° between the planes of the two rings. The crystal structure can be described by two types of crossed layers which are parallel to (110) and (1\overline{1}0).

Comment top

For a structurally simple group of compounds, chalcones have displayed an impressive array for biological activities, among which anti-malarial (Liu et al., 2003), anti protozoal (Li et al., 1995), anti-inflammatory (Hsieh et al., 1998), immunomodulatory (Barford et al., 2002), nitric oxid inhibition (Rojas et al., 2002), tyronase inhibition (Nerya et al., 2006), cytotoxic (Yang et al., 2000) and anticancer (Ducki et al., 1998) activities have been cited in literature.

Chalcone may be useful for the chemotherapy of leishmanisis among others (Lawrence et al., 2001), they are also used as antibiotics (Nielsen et al., 2005). They were synthesized by a base catalyzed Claisen-Schmidt condensation of aromatic aldehydes and ketones. A natural medicine genus Angelica is known to contain large number of naturally occurring chalcones (Sarker et al., 2004). Chalcone derivatives are recognized for NLO properties and have good crystallization ability (Goto et al., 1991; Indira et al., 2002; Sarojini et al., 2006).

Structure of few related chalcones viz., (2E) -1- (2,4-dichlorophenyl) -3-(2-hydrox-3-metoxyphenyl)prop -2-en-1-one (Yathirajan et al., 2007), (2E) -1- (3-hydroxyphenyl) -3-(4-methylphenyl)prop-2-en-1-one (Butcher et al., 2007), (2E)-3-(biphenyl-4-yl)-1-(4-methoxyphenyl)prop-2-en-1-one (Fischer et al., 2007).

The molecular structure of (I), and the atomic numbering used, is illustrated in Fig. 1. A diagram of the layered crystal packing in the unit cell of (I) is shown in Fig. 2. A substituted chalcone adopts an E configuration with respect to the C=C bond of the enone unit. The molecule is not planar, as can be seen from the dihedral angle of 6.21 (7)° between the two rings. The crystal structure can be described by two types of crossed layers, parallel to (110) and (1–10) respectively (Fig. 2).

The packing is stabilized by Van der Walls interactions and by C—H···π interactions resulting in the formation of three dimensional network (Table 1.).

Related literature top

For backround to the applications of chalcones, see: Liu et al. (2003); Li et al. (1995); Hsieh et al. (1998); Barford et al. (2002); Rojas et al. (2002); Nerya et al. (2006); Yang et al. (2000); Ducki et al. (1998); Goto et al. (1991); Indira et al. (2002); Lawrence et al. (2001); Nielsen et al. (2005); Sarker & Nahar (2004); Sarojini et al. (2006). For related structures, see: Yathirajan et al. (2007); Butcher et al. (2007); Fischer et al. (2007). Cg1 and Cg2 are the centroids of the C1–C6 and C11–C16 rings, respectively.

Experimental top

To a mixture of 2,6 dichlorobenzaldehyde (1.75 g, 0.01 mol) and 4-methoxyacetophenone (1.50 g, 0.01 mol) in ethanol 20 ml in the presence of a catalytic amount of sodium hydroxide solution (5 ml) was added slowly with stirring (6 h), the contents of the flask were poured into ice cold water (500 ml) and left to stand for 5 h. The resulting crude solid was filtered and purified by recrystallization in ethanol. Crystal suitable for x-ray analysis was grown by slow evaporation of an acetone solution at room temperature.

Refinement top

All H atoms were localized in Fourier maps but introduced in calculated positions and treated as riding on their parent C atoms with C—H = 0.95–0.98Å and Uiso(H) =1.2–1.5(carrier atom).

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SIR2002 (Burla et al., 2003); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999) and DIAMOND (Brandenburg & Berndt, 2001).

Figures top
[Figure 1] Fig. 1. (Farrugia, 1997) The structure of the title compound with the atomic labeling scheme. Displacements are drawn at the 50% probability level.
[Figure 2] Fig. 2. (Brandenburg & Berndt, 2001) A diagram of the layered crystal packing in (I), viewed down the c axis.
(E)-3-(2,6-Dichlorophenyl)-1-(4-methoxyphenyl)prop-2-en-1-one top
Crystal data top
C16H12Cl2O2F(000) = 632
Mr = 307.16Dx = 1.445 Mg m−3
Orthorhombic, P212121Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2abCell parameters from 3041 reflections
a = 6.4793 (2) Åθ = 2.4–27.4°
b = 12.9807 (5) ŵ = 0.46 mm−1
c = 16.7819 (8) ÅT = 100 K
V = 1411.46 (10) Å3Prism, colourless
Z = 40.37 × 0.28 × 0.2 mm
Data collection top
Bruker APEXII
diffractometer		2964 reflections with I > 2σ(I)
graphiteRint = 0.029
CCD rotation images, thin slices scansθmax = 27.4°, θmin = 3.5°
Absorption correction: multi-scan
(SADABS, Bruker, 1998)		h = −6→8
Tmin = 0.824, Tmax = 0.913k = −15→16
6643 measured reflectionsl = −20→21
3211 independent reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.036H-atom parameters constrained
wR(F2) = 0.090 w = 1/[σ2(Fo2) + (0.0409P)2 + 0.5074P]
where P = (Fo2 + 2Fc2)/3
S = 1.05(Δ/σ)max = 0.002
3211 reflectionsΔρmax = 0.51 e Å−3
182 parametersΔρmin = −0.20 e Å−3
0 restraintsAbsolute structure: Flack (1983), 1331 Friedel pairs
Primary atom site location: structure-invariant direct methodsFlack parameter: 0.01 (6)
Crystal data top
C16H12Cl2O2V = 1411.46 (10) Å3
Mr = 307.16Z = 4
Orthorhombic, P212121Mo Kα radiation
a = 6.4793 (2) ŵ = 0.46 mm−1
b = 12.9807 (5) ÅT = 100 K
c = 16.7819 (8) Å0.37 × 0.28 × 0.2 mm
Data collection top
Bruker APEXII
diffractometer		3211 independent reflections
Absorption correction: multi-scan
(SADABS, Bruker, 1998)		2964 reflections with I > 2σ(I)
Tmin = 0.824, Tmax = 0.913Rint = 0.029
6643 measured reflectionsθmax = 27.4°
Refinement top
R[F2 > 2σ(F2)] = 0.036H-atom parameters constrained
wR(F2) = 0.090Δρmax = 0.51 e Å−3
S = 1.05Δρmin = −0.20 e Å−3
3211 reflectionsAbsolute structure: Flack (1983), 1331 Friedel pairs
182 parametersFlack parameter: 0.01 (6)
0 restraints
Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s 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 > σ(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) top
xyzUiso*/Ueq
Cl10.49869 (7)1.03293 (4)0.58897 (3)0.02481 (12)
Cl50.06450 (7)0.84015 (4)0.35072 (3)0.02267 (12)
C10.2990 (3)0.95544 (14)0.55269 (13)0.0174 (4)
C20.1599 (3)0.91924 (15)0.60937 (13)0.0211 (4)
H20.17790.93630.6640.025*
C3−0.0051 (3)0.85821 (14)0.58604 (13)0.0226 (4)
H3−0.10010.83330.62460.027*
C4−0.0312 (3)0.83360 (14)0.50613 (12)0.0206 (4)
H4−0.14220.79070.48980.025*
C50.1068 (3)0.87235 (14)0.45044 (12)0.0167 (4)
C60.2774 (3)0.93459 (13)0.47063 (13)0.0149 (4)
C70.4050 (3)0.97926 (13)0.40676 (12)0.0150 (4)
H70.33540.99280.3580.018*
C80.6062 (3)1.00344 (13)0.40815 (13)0.0169 (4)
H80.68770.98710.45350.02*
C90.7012 (3)1.05587 (14)0.33855 (12)0.0172 (4)
O100.61836 (19)1.05435 (10)0.27255 (9)0.0215 (3)
C110.8991 (3)1.11288 (13)0.35089 (12)0.0154 (4)
C120.9741 (3)1.13891 (13)0.42704 (11)0.0164 (4)
H120.90171.11680.47320.02*
C131.1527 (3)1.19652 (14)0.43510 (12)0.0172 (4)
H131.20221.21390.48670.021*
C141.0073 (3)1.14718 (13)0.28402 (11)0.0170 (4)
H140.95691.1310.23240.02*
C151.1874 (3)1.20463 (14)0.29156 (12)0.0173 (4)
H151.261.2270.24550.021*
C161.2603 (3)1.22906 (14)0.36746 (12)0.0172 (4)
O171.4376 (2)1.28344 (10)0.38116 (8)0.0224 (3)
C181.5488 (3)1.32052 (14)0.31247 (13)0.0225 (4)
H18A1.57851.26280.27660.034*
H18B1.67861.35220.32970.034*
H18C1.46481.37180.28440.034*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.0219 (2)0.0314 (2)0.0211 (3)−0.0074 (2)−0.0005 (2)−0.0049 (2)
Cl50.0219 (2)0.0227 (2)0.0234 (3)−0.0029 (2)−0.0021 (2)−0.0059 (2)
C10.0151 (8)0.0157 (9)0.0215 (11)0.0023 (8)−0.0002 (8)0.0001 (8)
C20.0214 (10)0.0226 (10)0.0193 (11)0.0027 (9)0.0009 (8)0.0047 (8)
C30.0193 (9)0.0232 (9)0.0255 (11)−0.0005 (9)0.0070 (9)0.0083 (8)
C40.0156 (9)0.0156 (8)0.0305 (12)−0.0028 (8)0.0000 (8)0.0023 (8)
C50.0157 (9)0.0123 (8)0.0221 (11)0.0024 (8)−0.0027 (8)0.0005 (7)
C60.0129 (8)0.0116 (8)0.0203 (10)0.0030 (7)0.0014 (7)0.0009 (7)
C70.0188 (9)0.0112 (8)0.0150 (10)0.0024 (7)−0.0008 (8)0.0005 (8)
C80.0163 (9)0.0161 (9)0.0182 (11)0.0025 (7)−0.0013 (8)0.0034 (8)
C90.0160 (8)0.0161 (9)0.0195 (11)0.0034 (7)0.0020 (8)−0.0002 (8)
O100.0188 (6)0.0280 (7)0.0176 (8)−0.0035 (6)−0.0014 (6)0.0022 (6)
C110.0140 (8)0.0150 (8)0.0172 (10)0.0021 (7)0.0000 (8)0.0005 (8)
C120.0180 (9)0.0168 (9)0.0146 (10)0.0039 (8)0.0026 (7)0.0019 (7)
C130.0212 (9)0.0170 (9)0.0135 (10)0.0022 (8)−0.0034 (8)−0.0031 (7)
C140.0169 (8)0.0193 (9)0.0149 (9)0.0017 (9)−0.0016 (8)0.0009 (7)
C150.0170 (9)0.0185 (9)0.0163 (10)0.0003 (8)0.0022 (8)0.0040 (8)
C160.0166 (9)0.0121 (8)0.0228 (12)0.0005 (8)−0.0013 (7)0.0013 (8)
O170.0214 (7)0.0264 (7)0.0195 (8)−0.0088 (6)−0.0016 (6)0.0005 (6)
C180.0202 (10)0.0218 (9)0.0256 (11)−0.0072 (8)0.0001 (8)0.0037 (8)
Geometric parameters (Å, °) top
Cl1—C11.7484 (19)C9—C111.494 (3)
Cl5—C51.747 (2)C11—C141.396 (3)
C1—C21.392 (3)C11—C121.409 (3)
C1—C61.410 (3)C12—C131.384 (3)
C2—C31.387 (3)C12—H120.95
C2—H20.95C13—C161.397 (3)
C3—C41.389 (3)C13—H130.95
C3—H30.95C14—C151.391 (3)
C4—C51.388 (3)C14—H140.95
C4—H40.95C15—C161.395 (3)
C5—C61.410 (3)C15—H150.95
C6—C71.473 (3)C16—O171.368 (2)
C7—C81.342 (2)O17—C181.442 (2)
C7—H70.95C18—H18A0.98
C8—C91.485 (3)C18—H18B0.98
C8—H80.95C18—H18C0.98
C9—O101.231 (2)
C2—C1—C6122.56 (18)C8—C9—C11118.26 (17)
C2—C1—Cl1115.81 (16)C14—C11—C12118.64 (16)
C6—C1—Cl1121.59 (15)C14—C11—C9118.51 (18)
C3—C2—C1119.9 (2)C12—C11—C9122.73 (17)
C3—C2—H2120C13—C12—C11120.46 (17)
C1—C2—H2120C13—C12—H12119.8
C2—C3—C4119.84 (18)C11—C12—H12119.8
C2—C3—H3120.1C12—C13—C16120.05 (18)
C4—C3—H3120.1C12—C13—H13120
C5—C4—C3119.26 (17)C16—C13—H13120
C5—C4—H4120.4C15—C14—C11121.28 (18)
C3—C4—H4120.4C15—C14—H14119.4
C4—C5—C6123.41 (19)C11—C14—H14119.4
C4—C5—Cl5117.23 (14)C14—C15—C16119.28 (18)
C6—C5—Cl5119.36 (15)C14—C15—H15120.4
C1—C6—C5114.98 (18)C16—C15—H15120.4
C1—C6—C7125.42 (17)O17—C16—C15123.72 (18)
C5—C6—C7119.37 (18)O17—C16—C13116.00 (18)
C8—C7—C6128.68 (19)C15—C16—C13120.27 (17)
C8—C7—H7115.7C16—O17—C18117.23 (15)
C6—C7—H7115.7O17—C18—H18A109.5
C7—C8—C9119.76 (19)O17—C18—H18B109.5
C7—C8—H8120.1H18A—C18—H18B109.5
C9—C8—H8120.1O17—C18—H18C109.5
O10—C9—C8121.29 (17)H18A—C18—H18C109.5
O10—C9—C11120.44 (17)H18B—C18—H18C109.5
C6—C1—C2—C31.5 (3)C7—C8—C9—C11159.67 (16)
Cl1—C1—C2—C3179.21 (14)O10—C9—C11—C14−12.1 (3)
C1—C2—C3—C4−0.1 (3)C8—C9—C11—C14169.21 (16)
C2—C3—C4—C5−1.3 (3)O10—C9—C11—C12163.91 (17)
C3—C4—C5—C61.4 (3)C8—C9—C11—C12−14.8 (2)
C3—C4—C5—Cl5−179.22 (14)C14—C11—C12—C13−0.6 (2)
C2—C1—C6—C5−1.4 (3)C9—C11—C12—C13−176.57 (16)
Cl1—C1—C6—C5−178.94 (13)C11—C12—C13—C16−0.2 (3)
C2—C1—C6—C7173.05 (17)C12—C11—C14—C151.0 (2)
Cl1—C1—C6—C7−4.5 (3)C9—C11—C14—C15177.10 (16)
C4—C5—C6—C1−0.1 (2)C11—C14—C15—C16−0.5 (3)
Cl5—C5—C6—C1−179.47 (13)C14—C15—C16—O17178.75 (16)
C4—C5—C6—C7−174.87 (16)C14—C15—C16—C13−0.3 (3)
Cl5—C5—C6—C75.8 (2)C12—C13—C16—O17−178.48 (15)
C1—C6—C7—C835.1 (3)C12—C13—C16—C150.6 (3)
C5—C6—C7—C8−150.75 (19)C15—C16—O17—C182.6 (2)
C6—C7—C8—C9−175.13 (17)C13—C16—O17—C18−178.31 (16)
C7—C8—C9—O10−19.0 (3)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C4—H4···Cg1i0.952.843.727157
C7—H7···Cg2i0.952.853.360115
Symmetry codes: (i) x+1/2, −y−1/2, −z.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C4—H4···Cg1i0.952.843.727157
C7—H7···Cg2i0.952.853.360115
Symmetry codes: (i) x+1/2, −y−1/2, −z.
Acknowledgements top

The authors are grateful to Dr Thierry Roisnel, Centre de Diffractométrie X (CDIFX) de Rennes, Université de Rennes 1, France, for the data-collection facilities.

references
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