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Acta Crystallogr Sect E Struct Rep Online. 2010 May 1; 66(Pt 5): o1139.
Published online 2010 April 24. doi:  10.1107/S1600536810014364
PMCID: PMC2979294

(E)-1-(2,5-Dichloro-3-thien­yl)-3-[4-(dimethyl­amino)phen­yl]prop-2-en-1-one

Abstract

In the title compound, C15H13Cl2NOS, the benzene and thio­phene rings make a dihedral angle of 10.8 (1)°. The dimethyl­amino substituent and the α,β-unsaturated carbonyl group are almost coplanar with respect to the aromatic ring, forming dihedral angles of 4.73 (3)° and 5.0 (2)°, respectively. In the crystal structure, mol­ecules are connected into two-dimensional layers by weak C—H(...)Cl hydrogen bonds and C—Cl(...)O [Cl(...)O = 3.073 (2) Å] inter­actions. These layers are stacked with short C(meth­yl)–H(...)π contacts betweeen the layers.

Related literature

For applications of chalcone derivatives, see: Indira et al. (2002 [triangle]); Sarojini et al. (2006 [triangle]); Tomar et al. (2007 [triangle]).

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Object name is e-66-o1139-scheme1.jpg

Experimental

Crystal data

  • C15H13Cl2NOS
  • M r = 326.22
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-o1139-efi1.jpg
  • a = 7.2637 (9) Å
  • b = 8.1136 (9) Å
  • c = 13.478 (2) Å
  • α = 89.011 (9)°
  • β = 79.71 (1)°
  • γ = 73.07 (1)°
  • V = 747.2 (2) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 0.57 mm−1
  • T = 295 K
  • 0.6 × 0.3 × 0.3 mm

Data collection

  • Oxford Diffraction Xcalibur diffractometer with an Eos detector
  • Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009 [triangle]) T min = 0.785, T max = 1.000
  • 8710 measured reflections
  • 3152 independent reflections
  • 2403 reflections with I > 2σ(I)
  • R int = 0.018

Refinement

  • R[F 2 > 2σ(F 2)] = 0.038
  • wR(F 2) = 0.109
  • S = 1.10
  • 3152 reflections
  • 184 parameters
  • H-atom parameters constrained
  • Δρmax = 0.37 e Å−3
  • Δρmin = −0.40 e Å−3

Data collection: CrysAlis PRO (Oxford Diffraction, 2009 [triangle]); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SIR92 (Altomare et al., 1993 [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: Stereochemical Workstation Operation Manual (Siemens, 1989 [triangle]) and SHELXL97.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810014364/im2193sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810014364/im2193Isup2.hkl

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

Acknowledgments

CSC thanks the University of Mysore for research facilities.

supplementary crystallographic information

Comment

Chalcones derivatives are known for their interesting pharmacological activities. Radical quenching properties of the phenolic groups present in many chalcones have raised interest in using the compounds themselves or chalcone rich plant extracts as drugs or food preservatives. Apart from being biologically important compounds, chalcone derivatives show non-linear optical properties with excellent blue light transmittance and good crystallizability (Indira et al., 2002; Sarojini et al., 2006). They provide a necessary configuration to show NLO property with two planar rings connected by a conjugated double bond. Synthesis and antimicrobial evaluation of new chalcones containing a 2,5-dichlorothiophene moiety is reported (Tomar et al., 2007). Here, we report the synthesis and crystal structure of the new chalcone derivative, (2E)-1-(2,5-dichlorothiophen-3-yl)-3-(4-dimethylamino-phenyl)prop-2-en-1-one (I, Scheme 1) .

The molecule as a whole does not deviate significantly from planarity (Fig. 1). Dihedral angles between the constituent planar fragments are relatively small. The two ring planes of the phenyl and thiophene groups make a dihedral angle of 10.8 (1)°. The dimethylamino substituent and the α,β-unsaturated carbonyl moeity are inclined with respect to the phenyl ring plane by 4.73 (3)° and 5.0 (2)°, respectively. The bond lengths pattern within the C(=O)—C=C- fragment shows significant conjugation with shorter formal single bonds compared to formal double bonds that are longer than typical values.

In the crystal structure an intermolecular C–H···Cl hydrogen bond (H···Cl distance 2.72 Å, C–H···Cl angle 168°) and C—Cl···O interactions connect the molecules into approximately planar layers parallel to (101) (Fig. 2). The chlorine oxygen interaction also is almost linear (C2–Cl2···O6 angle of 167.6 (8)°) and relatively short (Cl2···O6 3.073 (2) Å). These layers are stacked on each other showing additional intermolecular C–H···π interactions with H16A···Cg distance of 3.01Å (Cg is the centroid of the phenyl ring).

Experimental

1-(2,5-Dichlorothiophen-3-yl)ethanone (1.95 g, 0.01 mol) was mixed with 4-dimethylamino)-benzaldehyde (1.49 g, 0.01 mol) and dissolved in ethanol (30 ml). 3 ml of KOH (50%) was added to this solution. The reaction mixture was stirred for 6 hours. The resulting crude solid was filtered, washed successively with distilled water and finally recrystallized from ethanol (95%) to give the pure chalcone. Crystals suitable for x-ray diffraction studies were grown by slow evaporation of solution in toluene (M.P.: 358 K).

Refinement

H atoms were placed in idealized positions and constrained to ride on their parent atoms, with C–H = 0.93 Å and Uiso(H) = 1.2 Ueq(C) for phenyl hydrogen and olefinic CH groups and with 0.96 Å and Uiso(H) = 1.5 Ueq(C) for CH3 groups.

Figures

Fig. 1.
Molecular structure of (I), showing 50% probability displacement ellipsoids and the atom-numbering scheme.
Fig. 2.
Crystal packing of (I) viewed along the b axis. C–H···Cl hydrogen bonds and C—Cl···O interactions are shown as dashed lines.
Fig. 3.
C–H···π interactions in the stack of molecules (I).

Crystal data

C15H13Cl2NOSZ = 2
Mr = 326.22F(000) = 336
Triclinic, P1Dx = 1.450 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 7.2637 (9) ÅCell parameters from 5611 reflections
b = 8.1136 (9) Åθ = 2.6–28.2°
c = 13.478 (2) ŵ = 0.57 mm1
α = 89.011 (9)°T = 295 K
β = 79.71 (1)°Block, yellow
γ = 73.07 (1)°0.6 × 0.3 × 0.3 mm
V = 747.2 (2) Å3

Data collection

Oxford Diffraction Xcalibur diffractometer with an Eos detector3152 independent reflections
Radiation source: Enhance (Mo) X-ray Source2403 reflections with I > 2σ(I)
graphiteRint = 0.018
Detector resolution: 16.1544 pixels mm-1θmax = 28.3°, θmin = 2.6°
ω scanh = −9→9
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)k = −10→10
Tmin = 0.785, Tmax = 1.000l = −17→17
8710 measured 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)] = 0.038Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.109H-atom parameters constrained
S = 1.10w = 1/[σ2(Fo2) + (0.0546P)2 + 0.1725P] where P = (Fo2 + 2Fc2)/3
3152 reflections(Δ/σ)max = 0.001
184 parametersΔρmax = 0.37 e Å3
0 restraintsΔρmin = −0.40 e Å3

Special details

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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
S10.67788 (8)0.11979 (8)1.11606 (4)0.05238 (18)
Cl20.49256 (8)0.25700 (9)0.94627 (4)0.0620 (2)
C20.6887 (3)0.2294 (3)1.00611 (14)0.0407 (4)
C30.8555 (3)0.2780 (2)0.98033 (14)0.0383 (4)
C40.9777 (3)0.2234 (3)1.05438 (15)0.0431 (5)
H4A1.09800.24431.05070.052*
Cl51.00237 (10)0.05512 (9)1.23148 (4)0.0699 (2)
C50.9014 (3)0.1398 (3)1.12908 (15)0.0454 (5)
C60.9255 (3)0.3667 (3)0.89011 (15)0.0432 (5)
O61.0970 (2)0.3669 (2)0.87491 (13)0.0636 (5)
C70.7927 (3)0.4499 (3)0.82226 (16)0.0473 (5)
H7A0.66210.45190.83780.057*
C80.8548 (3)0.5232 (3)0.73845 (16)0.0456 (5)
H8A0.98450.52420.72830.055*
C90.7452 (3)0.6010 (2)0.66156 (15)0.0412 (4)
C100.5490 (3)0.6086 (3)0.66361 (15)0.0435 (5)
H10A0.48200.56650.71880.052*
C110.4534 (3)0.6765 (3)0.58656 (15)0.0435 (5)
H11A0.32330.67950.59080.052*
C120.5478 (3)0.7420 (2)0.50101 (14)0.0399 (4)
C130.7440 (3)0.7332 (3)0.49862 (16)0.0489 (5)
H13A0.81250.77350.44320.059*
C140.8364 (3)0.6662 (3)0.57683 (16)0.0500 (5)
H14A0.96620.66410.57310.060*
N150.4527 (3)0.8088 (2)0.42422 (14)0.0527 (5)
C160.2469 (4)0.8283 (3)0.4313 (2)0.0669 (7)
H16A0.22670.71650.43080.100*
H16B0.20150.89060.37490.100*
H16C0.17560.89060.49290.100*
C170.5519 (4)0.8642 (4)0.33356 (17)0.0657 (7)
H17A0.59620.95940.34970.098*
H17B0.46360.89960.28680.098*
H17C0.66230.77070.30370.098*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
S10.0501 (3)0.0691 (4)0.0431 (3)−0.0253 (3)−0.0097 (2)0.0124 (3)
Cl20.0468 (3)0.0961 (5)0.0581 (4)−0.0360 (3)−0.0242 (3)0.0189 (3)
C20.0371 (10)0.0488 (11)0.0378 (10)−0.0123 (9)−0.0117 (8)0.0027 (8)
C30.0376 (10)0.0399 (10)0.0387 (10)−0.0103 (8)−0.0124 (8)0.0024 (8)
C40.0383 (10)0.0475 (12)0.0464 (11)−0.0125 (9)−0.0160 (9)0.0042 (9)
Cl50.0750 (4)0.0881 (5)0.0490 (3)−0.0178 (3)−0.0300 (3)0.0209 (3)
C50.0479 (11)0.0516 (12)0.0372 (10)−0.0104 (9)−0.0162 (9)0.0060 (9)
C60.0400 (10)0.0458 (11)0.0467 (11)−0.0139 (9)−0.0138 (9)0.0059 (9)
O60.0461 (9)0.0881 (12)0.0681 (11)−0.0317 (8)−0.0226 (8)0.0325 (9)
C70.0437 (11)0.0525 (12)0.0500 (12)−0.0165 (10)−0.0170 (9)0.0138 (10)
C80.0436 (11)0.0482 (12)0.0490 (12)−0.0165 (9)−0.0139 (9)0.0072 (9)
C90.0448 (11)0.0398 (11)0.0408 (10)−0.0144 (9)−0.0091 (8)0.0057 (8)
C100.0447 (11)0.0474 (12)0.0389 (10)−0.0165 (9)−0.0046 (8)0.0086 (9)
C110.0382 (10)0.0496 (12)0.0436 (11)−0.0148 (9)−0.0078 (8)0.0083 (9)
C120.0451 (11)0.0370 (10)0.0379 (10)−0.0119 (8)−0.0085 (8)0.0044 (8)
C130.0474 (12)0.0568 (13)0.0456 (12)−0.0226 (10)−0.0054 (9)0.0145 (10)
C140.0404 (11)0.0612 (14)0.0528 (13)−0.0217 (10)−0.0098 (9)0.0138 (10)
N150.0540 (11)0.0618 (12)0.0466 (10)−0.0205 (9)−0.0163 (8)0.0205 (8)
C160.0601 (15)0.0778 (17)0.0707 (16)−0.0228 (13)−0.0302 (13)0.0236 (13)
C170.0734 (17)0.0800 (17)0.0454 (13)−0.0247 (14)−0.0132 (12)0.0191 (12)

Geometric parameters (Å, °)

S1—C21.717 (2)C10—C111.371 (3)
S1—C51.717 (2)C10—H10A0.9300
Cl2—C21.7175 (19)C11—C121.411 (3)
C2—C31.366 (3)C11—H11A0.9300
C3—C41.433 (3)C12—N151.364 (3)
C3—C61.489 (3)C12—C131.401 (3)
C4—C51.333 (3)C13—C141.371 (3)
C4—H4A0.9300C13—H13A0.9300
Cl5—C51.718 (2)C14—H14A0.9300
C6—O61.226 (2)N15—C171.439 (3)
C6—C71.462 (3)N15—C161.443 (3)
C7—C81.335 (3)C16—H16A0.9600
C7—H7A0.9300C16—H16B0.9600
C8—C91.444 (3)C16—H16C0.9600
C8—H8A0.9300C17—H17A0.9600
C9—C141.391 (3)C17—H17B0.9600
C9—C101.403 (3)C17—H17C0.9600
C2—S1—C589.86 (10)C10—C11—C12121.54 (19)
C3—C2—S1113.70 (14)C10—C11—H11A119.2
C3—C2—Cl2130.86 (16)C12—C11—H11A119.2
S1—C2—Cl2115.43 (11)N15—C12—C13121.88 (18)
C2—C3—C4110.04 (18)N15—C12—C11121.47 (19)
C2—C3—C6130.73 (17)C13—C12—C11116.65 (18)
C4—C3—C6119.18 (17)C14—C13—C12120.89 (19)
C5—C4—C3113.12 (18)C14—C13—H13A119.6
C5—C4—H4A123.4C12—C13—H13A119.6
C3—C4—H4A123.4C13—C14—C9123.04 (19)
C4—C5—S1113.29 (15)C13—C14—H14A118.5
C4—C5—Cl5127.12 (17)C9—C14—H14A118.5
S1—C5—Cl5119.59 (13)C12—N15—C17121.73 (19)
O6—C6—C7121.58 (19)C12—N15—C16121.05 (19)
O6—C6—C3117.89 (17)C17—N15—C16117.22 (19)
C7—C6—C3120.54 (17)N15—C16—H16A109.5
C8—C7—C6121.49 (19)N15—C16—H16B109.5
C8—C7—H7A119.3H16A—C16—H16B109.5
C6—C7—H7A119.3N15—C16—H16C109.5
C7—C8—C9127.96 (19)H16A—C16—H16C109.5
C7—C8—H8A116.0H16B—C16—H16C109.5
C9—C8—H8A116.0N15—C17—H17A109.5
C14—C9—C10116.05 (18)N15—C17—H17B109.5
C14—C9—C8120.06 (18)H17A—C17—H17B109.5
C10—C9—C8123.80 (18)N15—C17—H17C109.5
C11—C10—C9121.81 (18)H17A—C17—H17C109.5
C11—C10—H10A119.1H17B—C17—H17C109.5
C9—C10—H10A119.1
C5—S1—C2—C30.36 (17)C6—C7—C8—C9176.1 (2)
C5—S1—C2—Cl2179.45 (13)C7—C8—C9—C14−177.7 (2)
S1—C2—C3—C4−0.3 (2)C7—C8—C9—C10−1.0 (4)
Cl2—C2—C3—C4−179.25 (16)C14—C9—C10—C110.0 (3)
S1—C2—C3—C6176.89 (17)C8—C9—C10—C11−176.8 (2)
Cl2—C2—C3—C6−2.0 (4)C9—C10—C11—C120.1 (3)
C2—C3—C4—C50.1 (3)C10—C11—C12—N15179.72 (19)
C6—C3—C4—C5−177.47 (18)C10—C11—C12—C130.3 (3)
C3—C4—C5—S10.1 (2)N15—C12—C13—C14179.7 (2)
C3—C4—C5—Cl5−179.88 (15)C11—C12—C13—C14−0.9 (3)
C2—S1—C5—C4−0.28 (18)C12—C13—C14—C91.0 (4)
C2—S1—C5—Cl5179.74 (14)C10—C9—C14—C13−0.5 (3)
C2—C3—C6—O6−166.3 (2)C8—C9—C14—C13176.4 (2)
C4—C3—C6—O610.7 (3)C13—C12—N15—C174.0 (3)
C2—C3—C6—C713.5 (3)C11—C12—N15—C17−175.4 (2)
C4—C3—C6—C7−169.47 (18)C13—C12—N15—C16−175.5 (2)
O6—C6—C7—C83.0 (3)C11—C12—N15—C165.2 (3)
C3—C6—C7—C8−176.8 (2)

Hydrogen-bond geometry (Å, °)

Cg is the centroid of the phenyl ring.
D—H···AD—HH···AD···AD—H···A
C16—H16B···Cl5i0.962.723.664 (2)168
C16—H16A···Cgii0.963.013.899 (3)155

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: IM2193).

References

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  • Sarojini, B. K., Narayana, B., Ashalatha, B. V., Indira, J. & Lobo, K. G. (2006). J. Cryst. Growth, 295, 54–59.
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