(E)-1-(2-Thien­yl)-3-(3,4,5-trimethoxy­phen­yl)prop-2-en-1-one

Thitipone Suwunwong; Suchada Chantrapromma; Paradorn Pakdeevanich; Hoong-Kun Fun

doi:10.1107/S1600536809021850

. 2009 Jun 13;65(Pt 7):o1575–o1576. doi: 10.1107/S1600536809021850

(E)-1-(2-Thienyl)-3-(3,4,5-trimethoxyphenyl)prop-2-en-1-one¹

Thitipone Suwunwong ^a, Suchada Chantrapromma ^a,^*,^‡, Paradorn Pakdeevanich ^b, Hoong-Kun Fun ^c,^§

PMCID: PMC2969210 PMID: 21582853

Abstract

The molecule of the title heteroaryl chalcone, C₁₆H₁₆O₄S, which consists of substituted thiophene and benzene rings bridged by the prop-2-en-1-one group, is slightly twisted. The dihedral angle between the thiophene and 3,4,5-trimethoxyphenyl rings is 12.18 (4)°. The three methoxy groups have two different conformations; two methoxy groups are coplanar [C—O—C—C torsion angles = −1.38 (12) and 0.47 (12)°] whereas the third is (-)-synclinal with the benzene ring. In the crystal structure, adjacent molecules are linked in a face-to-side manner into chains along the c axis by weak C—H⋯O(enone) interactions. These chains are stacked along the b axis by weak C—H⋯O(methoxy) interactions.

Related literature

For bond-length data, see: Allen et al. (1987 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For related structures, see: Chantrapromma et al. (2009 ▶); Patil et al. (2006 ▶; 2007 ▶); Suwunwong et al. (2009a ▶,b ▶). For background to and applications of chalcones, see: Dimmock et al. (1999 ▶); Go et al. (2005 ▶); Jung et al. (2008 ▶); Ni et al. (2004 ▶); Patil et al. (2007 ▶); Patil & Dharmaprakash (2008 ▶). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer, (1986 ▶).

Experimental

Crystal data

C₁₆H₁₆O₄S
M _r = 304.36
Orthorhombic,
a = 25.3323 (8) Å
b = 3.9816 (1) Å
c = 14.0163 (4) Å
V = 1413.73 (7) Å³
Z = 4
Mo Kα radiation
μ = 0.24 mm⁻¹
T = 100 K
0.58 × 0.31 × 0.21 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.872, T _max = 0.951
56940 measured reflections
7416 independent reflections
7177 reflections with I > 2σ(I)
R _int = 0.028

Refinement

R[F ² > 2σ(F ²)] = 0.033
wR(F ²) = 0.099
S = 1.10
7416 reflections
193 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.66 e Å⁻³
Δρ_min = −0.54 e Å⁻³
Absolute structure: Flack (1983 ▶), 3588 Friedel pairs
Flack parameter: 0.04 (4)

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT (Bruker, 2005 ▶); data reduction: SAINT; 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, 2009 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809021850/sj2627sup1.cif

e-65-o1575-sup1.cif^{(19.4KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809021850/sj2627Isup2.hkl

e-65-o1575-Isup2.hkl^{(362.9KB, 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
C1—H1A⋯O1ⁱ	0.93	2.52	3.1827 (14)	129
C15—H15C⋯O3ⁱⁱ	0.96	2.39	3.3340 (11)	169

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Symmetry codes: (i) Inline graphic ; (ii) .

Acknowledgments

Financial support from the Prince of Songkla University through the Crystal Materials Research Unit is gratefully acknowledged. TS thanks the Graduate School, Prince of Songkla University, for partial financial support. The authors also thank Universiti Sains Malaysia for the Research University Golden Goose grant No. 1001/PFIZIK/811012.

supplementary crystallographic information

Comment

Chalcone or 1,3-diaryl-2-propen-1-one, originally isolated from natural sources, and its derivatives are known to display a variety of biological activities, demonstrating analgesic, anti-inflammatory, antibacterial and antimycotic properties (Dimmock et al., 1999; Go et al., 2005; Ni et al., 2004). Moreover synthetic chalcones have also been found to be non-linear optical (NLO) (Patil & Dharmaprakash, 2008) and electro-active fluorescent materials (Jung et al., 2008). We have previously reported the synthesis and crystal structures of chalcone derivatives (Chantrapromma et al., 2009; Suwunwong et al., 2009a, b). Our research into the NLO and biological properties of chalcone derivatives led us to synthesize the title heteroaryl chalcone (I). (I) crystallizes in the non-centrosymmetric orthorhombic space group Pna2₁ and should therefore exhibit second-order nonlinear optical properties.

The molecule of the title heteroaryl chalcone (Fig. 1) exists in an E configuration with respect to the C6═C7 double bond [1.3437 (11) Å] with a C5–C6–C7–C8 torsion angle 176.81 (8)°. The whole molecule is twisted as shown by the interplanar angle between thiophene and 3,4,5-trimethoxyphenyl rings being 12.18 (4)°. The propenone unit (C5—C7/O1) is also twisted with the O1–C5–C6–C7 torsion angle 10.94 (15)°. The three substituted methoxy groups of 3,4,5-trimethoxyphenyl unit have two different orientations: two methoxy groups (at the C10 and C12 positions) are co-planar with the phenyl ring with torsion angles C14–O2–C10–C9 = -1.38 (12)° and C16–O4–C12–C13 = 0.47 (12)° whereas the one at C11 is (-)-syn-clinally attached with the C15–O3–C11–C12 torsion angle -76.76 (10)°. In the structure, weak intramolecular C7—H7A···O1 and C15—H15B···O4 interactions generate S(5) and S(6) ring motifs, respectively (Bernstein et al., 1995). The bond distances have normal values (Allen et al., 1987) and bond lengths and angles are comparable with closely related structures (Chantrapromma et al., 2009; Patil et al., 2006; 2007; Suwunwong et al., 2009a, b).

In the crystal packing, the adjacent molecules are linked in a face-to-side manner into chains along the c axis through the enone unit by weak C1—H1A···O1 interactions (Fig. 2, Table 1). Weak C15—H15C···O3 interactions involving one of methoxy groups further stack these chains along the b axis (Fig. 3, Table 1).

Experimental

The title compound was synthesized by the condensation of 3,4,5-trimethoxybenzaldehyde (0.40 g, 2 mmol) with 2-acetylthiophene (0.35 ml, 2 mmol) in ethanol (30 ml) in the presence of 30% NaOH (aq) (5 ml). After stirring for 3 h in ice bath at 278 K, the resulting pale yellow solid was collected by filtration, washed with distilled water, dried in air and purified by repeated recrystallization from acetone (72% yield). Pale yellow block-shaped single crystals of the title compound suitable for x-ray structure determination were recrystalized from acetone/ethanol (1:1 v/v) by the slow evaporation of the solvent at room temperature after several days, Mp. 420–421 K.