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

Hoong-Kun Fun; P S Patil; S M Dharmaprakash; Suchada Chantrapromma; Ibrahim Abdul Razak

doi:10.1107/S1600536808026524

. 2008 Aug 23;64(Pt 9):o1814–o1815. doi: 10.1107/S1600536808026524

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

Hoong-Kun Fun ^a,^*, P S Patil ^b,^‡, S M Dharmaprakash ^c, Suchada Chantrapromma ^d,^§, Ibrahim Abdul Razak ^a

PMCID: PMC2960483 PMID: 21201791

Abstract

In the title chalcone derivative, C₁₃H₈Cl₂OS, the prop-2-en-1-one unit and the thiophene and 2,4-dichlorophenyl rings are each essentially planar. The interplanar angle between the thiophene and 2,4-dichlorophenyl rings is 19.87 (6)°. Weak intramolecular C—H⋯O and C—H⋯Cl interactions involving the prop-2-en-1-one unit generate an S(5)S(5) ring motif. In the crystal structure, molecules are linked into head-to-tail zigzag chains along the a axis and adjacent chains are cross-linked. These cross-linked chains are arranged into sheets parallel to the ab plane. The crystal structure is stabilized by weak C—H⋯O, C—H⋯Cl and C—H⋯π interactions. A π–π interaction was also observed with a centroid–centroid distance of 3.6845 (6) Å.

Related literature

For details of hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For bond-length data, see: Allen et al. (1987 ▶). For related structures, see, for example: Fun et al. (2008a ▶,b ▶). For background on the applications of substituted chalcones, see, for example: Agrinskaya et al. (1999 ▶); Chopra et al. (2007 ▶); Goto et al. (1991 ▶); Gu et al. (2008a ▶,b ▶,c ▶); Patil et al. (2007a ▶,b ▶,c ▶); Sarojini et al. (2006 ▶); Wang et al. (2004 ▶).

Experimental

Crystal data

C₁₃H₈Cl₂OS
M _r = 283.16
Monoclinic,
a = 9.5701 (4) Å
b = 13.9544 (6) Å
c = 10.4748 (4) Å
β = 118.735 (3)°
V = 1226.59 (9) Å³
Z = 4
Mo Kα radiation
μ = 0.68 mm⁻¹
T = 100.0 (1) K
0.58 × 0.24 × 0.13 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.695, T _max = 0.919
41878 measured reflections
4435 independent reflections
3831 reflections with I > 2σ(I)
R _int = 0.031

Refinement

R[F ² > 2σ(F ²)] = 0.029
wR(F ²) = 0.082
S = 1.06
4435 reflections
162 parameters
H-atom parameters constrained
Δρ_max = 0.60 e Å⁻³
Δρ_min = −0.28 e Å⁻³

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: APEX2; data reduction: SAINT (Bruker, 2005 ▶); program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2003 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808026524/ww2127sup1.cif

e-64-o1814-sup1.cif^{(17.3KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808026524/ww2127Isup2.hkl

e-64-o1814-Isup2.hkl^{(217.3KB, hkl)}

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3A⋯O1ⁱ	0.93	2.52	3.4512 (17)	175
C7—H7A⋯Cl1	0.93	2.68	3.0573 (11)	105
C7—H7A⋯O1	0.93	2.48	2.8116 (17)	101
C10—H10A⋯Cg1ⁱⁱ	0.93	3.33	3.8233 (13)	115
C12—H12A⋯Cg1ⁱⁱⁱ	0.93	2.87	3.6907 (13)	148

Open in a new tab

Symmetry codes: (i) Inline graphic ; (ii) ; (iii) . Cg1 is the centroid of the S1/C1–C4 ring.

Acknowledgments

This work is supported by the Department of Science and Technology (DST), Government of India under grant No. SR/S2/LOP-17/2006. IAR and HKF thank Universiti Sains Malaysia and the Malaysian Government for the FRGS research grant No. 203/PFIZIK/671064. SC thanks Prince of Songkla University for generous support. The authors also thank Universiti Sains Malaysia for the Research University Golden Goose grant No. 1001/PFIZIK/811012.

supplementary crystallographic information

Comment

In the last decades, the second-order nonlinear optical properties of chalcone derivatives have been widely investigated due to their possible applications in a variety of optoelectronic and photonic applications (Agrinskaya et al., 1999; Goto et al., 1991; Patil et al., 2007a, b, c; Sarojini et al., 2006; Wang et al., 2004). These derivatives also exhibit the optical limiting property which is a requirement of protecting the human eye or artificial optical sensor from damaging high-energy lasers (Gu et al., 2008a, b, c). In our continuing systematic study on chalcone derivatives, we report here the structure of the title compound.

In the structure of the title chalcone derivative (Fig. 1), bond lengths and angles are in normal ranges (Allen et al., 1987) and comparable to those in related structures (Fun et al., 2008a, b). The prop-2-en-1-one unit (O1/C5–C7), the thiophene ring and the 2,4-dichlorophenyl ring are individually essentially planar, with maximum deviations of 0.003 (1), 0.024 (1), -0.007 (1)Å for atom C4, C7 and C11, respectively. The total molecule is slightly twisted as indicated by the dihedral angles between the least-squares plane through the prop-2-en-1-one unit with the thiophene and 2,4-dichlorophenyl rings being 7.89 (7)° and 22.45 (7)°, and that between the thiophene and 2,4-dichlorophenyl rings being 19.87 (6)°.

In the structure, both weak intramolecular C7—H7A···O1 and C7—H7A···Cl1 interactions (Table 1) generate S(5) ring motifs (Bernstein et al., 1995). In the crystal structure (Fig. 2) the molecules are linked in head-to-tail zigzag chains along the a-axis by weak C—H···Cl interactions and the adjacent chains were cross-linked by weak C—H···O interactions. These cross-linked chains are arranged into sheets parallel to the ab plane. The crystal is stabilized by weak C—H···O, C—H···Cl and C—H···π interactions (Table 1), π···π interaction was also observed with the Cg₂···Cg₂ distance of 3.6845 (6)Å (symmetry code: -x,1 - y, 1 - z); Cg₁ and Cg₂ are the centroids of S1/C1–C4 and C8–C13 rings.

Experimental

The title compound was synthesized by the condensation of 2,4-dichlorobenzaldehyde (0.01 mol, 1.75 g) with 2-acetylthiophene (0.01 mol, 1.07 ml) in methanol (60 ml) in the presence of a catalytic amount of sodium hydroxide solution (5 ml, 30%). After 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 dried. Needle colorless single crystals of the title compound suitable for X-Ray structure determination were grown by slow evaporation of the methanol solution at room temperature.