1,5-Bis(thio­phen-2-yl)-3-(2,4,5-trimeth­oxy­phen­yl)pentane-1,5-dione

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

doi:10.1107/S160053681104846X

. 2011 Nov 25;67(Pt 12):o3416–o3417. doi: 10.1107/S160053681104846X

1,5-Bis(thiophen-2-yl)-3-(2,4,5-trimethoxyphenyl)pentane-1,5-dione

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

PMCID: PMC3239053 PMID: 22199901

Abstract

In the title 1,5-diketone compound, C₂₂H₂₂O₅S₂, the benzene ring makes dihedral angles of 41.51 (6) and 25.83 (6)° with the two thiophene rings, while the dihedral angle between the thiophene rings is 26.67 (7)°. An intramolecular C—H⋯O interaction generates an S(9) ring motif. In the crystal, molecules are linked into a three-dimensional network by weak C—H⋯O and C—H⋯π interactions, and a π–π interaction with a centroid–centroid distance of 3.6527 (8) Å.

Related literature

For bond-length data, see: Allen et al. (1987 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For background and applications of 1,5-diketone compounds, see: Alagarsamy et al. (2007 ▶); Favaro et al. (2002 ▶); Harrowven & Hannam (1999 ▶); Pillai et al. (2004 ▶); Rai et al. (2008 ▶). For the preparation of the title compound, see: Suwunwong et al. (2011 ▶). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986 ▶).

Experimental

Crystal data

C₂₂H₂₂O₅S₂
M _r = 430.54
Monoclinic,
a = 16.1955 (2) Å
b = 7.5777 (1) Å
c = 16.7706 (2) Å
β = 93.490 (1)°
V = 2054.35 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.29 mm⁻¹
T = 100 K
0.26 × 0.20 × 0.18 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T _min = 0.928, T _max = 0.949
23337 measured reflections
6027 independent reflections
4962 reflections with I > 2σ(I)
R _int = 0.030

Refinement

R[F ² > 2σ(F ²)] = 0.038
wR(F ²) = 0.102
S = 1.04
6027 reflections
265 parameters
H-atom parameters constrained
Δρ_max = 0.43 e Å⁻³
Δρ_min = −0.46 e Å⁻³

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); 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 datablock(s) global, I. DOI: 10.1107/S160053681104846X/is5007sup1.cif

e-67-o3416-sup1.cif^{(22.3KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681104846X/is5007Isup2.hkl

e-67-o3416-Isup2.hkl^{(295.1KB, hkl)}

Supplementary material file. DOI: 10.1107/S160053681104846X/is5007Isup3.cml

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

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

Cg2 is the centroid of the C14–C19 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2A⋯O2ⁱ	0.95	2.57	3.5002 (18)	166
C3—H3A⋯O2	0.95	2.48	3.3677 (17)	156
C8—H8B⋯O1ⁱⁱ	0.99	2.58	3.3154 (16)	131
C21—H21A⋯O1ⁱⁱⁱ	0.98	2.57	3.0692 (17)	112
C22—H22A⋯O1^iv	0.98	2.39	3.3489 (16)	165
C21—H21B⋯Cg2^v	0.98	2.91	3.8317 (16)	158

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

Acknowledgments

TS thanks the Crystal Materials Research Unit for financial support. NW thanks the Prince of Songkla University for a postdoctoral fellowship. The authors also thank the Prince of Songkla University and Universiti Sains Malaysia for the Research University Grant No. 1001/PFIZIK/811160.

supplementary crystallographic information

Comment

Ketones are obviously one of the most important compounds in organic chemistry. There are many interesting applications of the compounds with the ketone group and the heterocyclic unit, which exhibit not only bioactivity such as antibacterial (Rai et al., 2008), anti-inflammatory (Pillai et al., 2004) and analgesic (Alagarsamy et al., 2007) activities, but also fluorescent property (Favaro et al., 2002). The 1,5-diketone compound is conventionally prepared by the oxidative cleavage of cyclopentenes or the conjugate addition of enolates to α,β-unsaturated ketones (Harrowven & Hannam, 1999).

In the molecule of the title compound (Fig. 1), the pentane-1,5-dione unit (C5–C9/O1/O2) is puckered with the torsion angles C5–C6–C7–C8 = 170.36 (10)° and C6–C7–C8–C9 = -71.81 (13)°, making the two ketone groups pointing towards opposite directions. A weak intramolecular C3—H3A···O2 interaction (Table 1) which generates an S(9) ring motif (Bernstein et al., 1995) helps to stabilize this conformation. The dihedral angle between the two thiophene rings is 26.67 (7)°. The 2,4,5-trimethoxyphenyl ring makes dihedral angles of 41.51 (6) and 25.83 (6)° with the S1/C1–C4 and S2/C10–C13 thiophene rings, respectively. The three substituted methoxy groups of 2,4,5-trimethoxyphenyl unit have two different orientations in which the ortho- and para-methoxy groups (at atom C15 and C17 positions) are co-planar with the phenyl ring with torsion angles C20–O3–C15–C16 = -0.50 (18)° and C21–O4–C17–C18 = 179.46 (12)° whereas the meta-methoxy (at atom C18) is twisted with the torsion angle C22–O5–C18–C19 = 10.08 (19)° The bond distances in (I) are in normal ranges (Allen et al., 1987).

In the crystal packing (Fig. 2), the molecules are linked into a three dimensional network through the enone unit by weak C—H···O interactions (Table 1), a weak C—H···π interaction (Table 1) and a π–π interaction with a Cg1···Cg1 distance of 3.6527 (8) Å; Cg1 is the centroid of S1/C1–C4 thiophene ring.

Experimental

The title compound (I) is a symmetrical 1,5-diketone compound which was alternatively synthesized by the stirring of (E)-1-(2-thitenyl)-3-(2,4,5-trimethoxyphenyl)prop-2-en-1-one (0.57 g, 1.5 mmol) (Suwunwong et al., 2011) in methanol (15 ml) with a freshly prepared sodium methoxide (1.5 mmol of sodium in 40 ml of methanol). Excess malononitrile (0.20 g, 3.0 mmol) was then added with continuous stirring at room temperature until the precipitate separated out. The resulting solid was filtered. Colorless single crystals of the title compound suitable for X-ray structure determination was obtained by recrystalization from acetone/methanol (1:1 v/v) by the slow evaporation of the solvent at room temperature after several days.