(Z)-3-(9-Anthr­yl)-1-(2-thien­yl)prop-2-en-1-one

Hoong-Kun Fun; Thitipone Suwunwong; Nawong Boonnak; Suchada Chantrapromma

doi:10.1107/S1600536809031900

. 2009 Aug 15;65(Pt 9):o2168–o2169. doi: 10.1107/S1600536809031900

(Z)-3-(9-Anthryl)-1-(2-thienyl)prop-2-en-1-one¹

Hoong-Kun Fun ^a,^*,^‡, Thitipone Suwunwong ^b, Nawong Boonnak ^b, Suchada Chantrapromma ^b,^§

PMCID: PMC2969873 PMID: 21577575

Abstract

There are two crystallographically independent molecules in the asymmetric unit of the title heteroaryl chalcone, C₂₁H₁₄OS: the dihedral angle between the thiophene and anthracene rings is 75.07 (17)° in one molecule and 76.32 (17)° in the other. The crystal structure is consolidated by short C⋯O [3.348 (5)–3.394 (5) Å], C⋯S [3.607 (5)–3.666 (5) Å] and S⋯O [2.926 (3) Å] contacts, as well as by C—H⋯π and π–π interactions [Cg⋯Cg = 3.745 (3) Å].

Related literature

For related structures, see: Chantrapromma et al. (2009 ▶); Suwunwong et al. (2009a ▶,b ▶). For background to and applications of chalcones, see: Oliveira et al. (2007 ▶); Patil & Dharmaprakash (2008 ▶); Saydam et al. (2003 ▶); Svetlichny et al. (2007 ▶). For the stability of the temperature controller used in the data collection, see Cosier & Glazer, (1986 ▶).

Experimental

Crystal data

C₂₁H₁₄OS
M _r = 314.39
Orthorhombic,
a = 14.6675 (2) Å
b = 5.5096 (1) Å
c = 37.9823 (4) Å
V = 3069.43 (8) Å³
Z = 8
Mo Kα radiation
μ = 0.21 mm⁻¹
T = 100 K
0.30 × 0.12 × 0.10 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.939, T _max = 0.979
28929 measured reflections
6662 independent reflections
5348 reflections with I > 2σ(I)
R _int = 0.055

Refinement

R[F ² > 2σ(F ²)] = 0.065
wR(F ²) = 0.200
S = 1.06
6662 reflections
391 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 1.58 e Å⁻³
Δρ_min = −0.82 e Å⁻³
Absolute structure: Flack (1983 ▶), 3093 Friedel pairs
Flack parameter: 0.09 (15)

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/S1600536809031900/tk2522sup1.cif

e-65-o2168-sup1.cif^{(29.6KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809031900/tk2522Isup2.hkl

e-65-o2168-Isup2.hkl^{(326.1KB, 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
C3A—H3AA⋯Cg3ⁱ	0.93	2.99	3.679 (5)	132
C10A—H10A⋯Cg2ⁱⁱ	0.93	2.95	3.694 (5)	138
C10B—H10B⋯Cg5ⁱ	0.93	2.93	3.594 (5)	129
C15A—H15A⋯Cg3ⁱⁱⁱ	0.93	2.76	3.550 (5)	143
C15B—H15B⋯Cg6ⁱⁱⁱ	0.93	2.94	3.689 (5)	139
C19A—H19A⋯Cg4	0.93	2.72	3.486 (5)	140
C19B—H19B⋯Cg1ⁱⁱⁱ	0.93	2.72	3.458 (5)	137

Open in a new tab

Symmetry codes: (i) Inline graphic ; (ii) ; (iii) . Cg1, Cg2, Cg3, Cg4, Cg5 and Cg6 are the centroids of the S1A/C18A–C21A, C1A–C6A, C8A–C13A, S1B/C18B–C21B, C1B–C6B and C8B–C13B rings, respectively.

Acknowledgments

The authors thank the Thailand Research Fund (TRF) for research grant (RSA 5280033) and Prince of Songkla University for financial support through the Crystal Materials Research Unit. The authors also thank Universiti Sains Malaysia for a Research University Golden Goose grant No. 1001/PFIZIK/811012.

supplementary crystallographic information

Comment

Chalcones have been studied for their chemical and biological activities for a long time. They have a wide range of applications such as in non-linear optical (NLO) materials (Patil & Dharmaprakash, 2008), fluorescent materials (Svetlichny et al., 2007) and for showing various biological activities (Saydam et al., 2003). The anthracene moieties are well known for their high absorption co-efficients as well as their high fluorescence yields (Oliveira et al., 2007). These interesting properties has lead us to synthesize the title heteroaryl chalcone derivative, (I), which contains the donor sub-unit (anthracene) and fluorophore (thiophene) in order to study its NLO and fluorescent properties. We have previously synthesized and reported the crystal structures of chalcones and heteroaryl chalcone derivatives (Chantrapromma et al., 2009; Suwunwong et al., 2009a, b) which exist in the E configuartion. Herein, we report the crystal structure of the (I) which is in the Z configuration. Compound (I) crystallizes in the non-centrosymmetric orthorhombic space group Pna2₁ and therefore, it should exhibit second-order nonlinear optical properties. Moreover, (I) also shows interesting fluorescence properties which will be reported elsewhere.

The asymmetric unit of (I) contains two molecules, A and B, with the same configuration but with slight differences in bond lengths and angles. The molecule of (I)(Fig. 1) exists in an Z configuration with respect to the C15=C16 double bond [1.360 (6) Å in molecule A and 1.331 (6) Å in molecule B]; the C14–C15–C16–C17 torsion angle = -3.7 (7)° in molecule A [-4.0 (7)° in molecule B]. The anthracene unit is essentially planar with the greatest deviation of 0.089 (5) Å at atom C11A [0.086 (5)Å at atom C3B]. The total molecule is twisted as the interplanar angle between thiophene and anthracene rings is 75.07 (17)° and the mean plane through the prop-2-en-1-one unit (C15–C17/O1) makes interplanar angles of 13.1 (3) and 71.2 (3)° with the thiophene and anthracene rings, respectively [the corresponding values are 76.32 (17), 15.2 (3) and 72.3 (3)° in molecule B]. The bond distances are comparable with related structures (Chantrapromma et al., 2009; Suwunwong et al., 2009a, b).

In the crystal packing, the molecules are connected by short C···O [3.348 (5)–3.394 (5) Å], C···S [3.607 (5)–3.666 (5) Å], and S···O [2.926 (3) Å] contacts. The crystal structure is further stabilized by C—H···π interactions (Table 1) and π–π interactions with the Cg₁···Cg₄ⁱ distance being 3.745 (3) Å (i: 1/2 + x, -y + 1/2, z); Cg₁ and Cg₄ are the centroids of the S1A/C18A–C21A and S1B/C18B–C21B rings, respectively.

Experimental

Compound (I) was synthesized by the condensation of anthracene-9-carbaldehyde (2 mmol, 0.41 g) with 2-acetylthiophene (2 mmol, 0.22 ml) in ethanol (30 ml) in the presence of NaOH (5 ml, 30 %). After stirring for 2 h, a yellow solid appeared which was then collected by filtration, washed with distilled water, dried and purified by repeated recrystallization using ethanol/acetone in a 1:5 ratio as solvent. Orange block-shaped crystals of (I) were obtained from hot ethanol by the slow evaporation of the solvent held at room temperature for several days; M.p. 391–392 K.