A second ortho­rhom­bic polymorph of (Z)-3-(9-anthr­yl)-1-(2-thien­yl)prop-2-en-1-one

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

doi:10.1107/S1600536810000061

. 2010 Jan 9;66(Pt 2):o312–o313. doi: 10.1107/S1600536810000061

A second orthorhombic polymorph of (Z)-3-(9-anthryl)-1-(2-thienyl)prop-2-en-1-one¹

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

PMCID: PMC2979950 PMID: 21579743

Abstract

The title heteroaryl chalcone, C₂₁H₁₄OS, is a second orthorhombic polymorph which crystallizes in the space group P2₁2₁2₁. The structure was previously reported [Fun et al. (2009 ▶). Acta Cryst. E65, o2168-o2169] in the space group Pna2₁. The bond distances and angles are similar in both structures. In contrast, the overall crystal packing is different from that in the first orthorhombic Pna2₁ polymorph in which molecules were stacked into columns along the b axis and the thiophene units of two adjacent columns were stacked in a head to tail fashion. In the present polymorph, molecules are found to dimerize through a weak S⋯S interaction [3.6513 (7) Å] and these dimers are arranged into sheets parallel to the bc plane. There are no classical hydrogen bonds in the packing which features short C⋯O [3.2832 (2)–3.6251 (9) Å], C⋯S [3.4879 (17)–3.6251 (19) Å] and S⋯O [2.9948 (16) Å] contacts, together with C—H⋯π interactions. Similar contacts were found in the other polymorph.

Related literature

For bond-length data, see: Allen et al. (1987 ▶). For the structure of the first polymorph, see: Fun et al. (2009 ▶). For background to and applications of chalcones, see: Chantrapromma et al. (2009 ▶); Patil & Dharmaprakash (2008 ▶); Saydam et al. (2003 ▶); Suwunwong et al. (2009 ▶); 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 = 314.38
Orthorhombic,
a = 5.5116 (1) Å
b = 14.8497 (2) Å
c = 18.3625 (3) Å
V = 1502.89 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.22 mm⁻¹
T = 100 K
0.50 × 0.19 × 0.11 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.900, T _max = 0.977
14062 measured reflections
4354 independent reflections
4035 reflections with I > 2σ(I)
R _int = 0.025

Refinement

R[F ² > 2σ(F ²)] = 0.042
wR(F ²) = 0.108
S = 1.05
4354 reflections
254 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.79 e Å⁻³
Δρ_min = −0.62 e Å⁻³
Absolute structure: Flack (1983 ▶), 1830 Friedel pairs
Flack parameter: 0.04 (8)

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/S1600536810000061/sj2716sup1.cif

e-66-0o312-sup1.cif^{(20.4KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810000061/sj2716Isup2.hkl

e-66-0o312-Isup2.hkl^{(213.4KB, hkl)}

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

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

Cg ₁, Cg ₂ and Cg ₃ are the centroids of the S1/C18–C21, C1–C6 and C8–C13 rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C5—H5A⋯Cg1ⁱ	0.91 (3)	2.64 (3)	3.443 (2)	149 (2)
C15—H15A⋯Cg2ⁱⁱ	0.95 (2)	2.74 (2)	3.565 (2)	146.4 (17)
C21—H21A⋯Cg3ⁱⁱⁱ	1.04 (3)	2.91 (3)	3.711 (2)	134.4 (19)

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

Acknowledgments

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

supplementary crystallographic information

Comment

In continuation of our study of chalcone derivatives (Chantrapromma et al., 2009; Fun et al., 2009; Suwunwong et al., 2009) which can be used for non-linear optical (NLO) materials (Patil & Dharmaprakash, 2008), fluorescent materials (Svetlichny et al., 2007) and bioactive compounds (Saydam et al., 2003), the title heteroaryl chalcone (I) was synthesized and its crystal structure was previously reported in the orthorhombic space group Pna2₁ (Fun et al., 2009). In the present work, the compound crystallized in the orthorhombic space group P2₁2₁2₁ from an ethanol/acetone (1:1) solvent mixture, while the crystal of the Pna2₁ form crystallized from hot ethanol. (I) exhibits fluorescence with the maximum emission at 402 nm when the compound is excited at 335 nm.

The molecule of (I) (Fig. 1) exists in an Z configuration with respect to the C15═C16 double bond and the torsion angle C14–C15–C16–C17 = -2.9 (3)° [compared to -3.7 (7)° in one molecule and -4.0 (7)° in the other in the Pna2₁ polymorph which contains two molecules in an asymmetric unit]. The molecule of the present polymorph is less twisted as indicated by the interplanar angles between thiophene and anthracene rings being 56.36 (7)° and the least squares plane through the prop-2-en-1-one unit (C15–C17/O1) makes interplanar angles of 12.2 and 68.00 (11)° with the thiophene and anthracene rings, respectively [the corresponding values are 75.07 (17), 13.1 (3) and 71.2 (3)° in one molecule and 76.32 (17), 15.2 (3) and 72.3 (3)° in the other for the Pna2₁ polymorph]. Bond distances are within normal ranges (Allen et al., 1987).

In the crystal packing (Fig. 2), molecules are found to dimerize through a non-bonding S···S interaction [S···S = 3.6513 (7) Å]. The dimers are arranged into sheets parallel to the bc plane. These sheets are stacked along the a axis. The intermolecular interactions and short contacts are almost similar in both polymorph. There is no classic hydrogen bond and the crystal is consolidated by short C···O [3.2832 (2)–3.6251 (9) Å], C···S [3.4879 (17)–3.6251 (19) Å] and S···O [2.9948 (16) Å] contacts, as well as C—H···π interactions (Table 1); Cg₁, Cg₂ and Cg₃ are the centroids of the S1/C18–C21, C1–C6 and C8–C13 rings, respectively.

Experimental

The title compound was synthesized as reported by Fun et al. (2009). Yellow block-shaped single crystals of the title compound suitable for x-ray structure determination were recrystallized from ethanol/acetone (1:1 v/v) by slow evaporation of the solvent at room temperature over several days, Mp. 400–401 K.