(E,E)-1,5-Di-2-thienylpenta-1,4-dien-3-one

Abstract

In the title compound, C₁₃H₁₀OS₂, the dihedral angle between the thio­phene rings is 14.3 (1)°. The mol­ecular structure is stabilized by C—H⋯π inter­actions between a thio­phene H atom and an adjacent thio­phene ring, and by inter­molecular C—H⋯O hydrogen bonds.

Related literature

For the bioactivity of chalcones, see: Go et al. (2005 ▶). For uses in organic solid-state photochemistry, see: Gould et al. (1995 ▶); For a related structure, see: Arshad et al. (2008 ▶). For the non-linear optical properties of bis-chalcones, see: Uchida et al. (1998 ▶).

Experimental

Crystal data

• C₁₃H₁₀OS₂

• M _r = 246.35

• Orthorhombic,

• a = 12.1141 (4) Å

• b = 7.4449 (3) Å

• c = 27.246 (1) Å

• V = 2457.27 (16) ų

• Z = 8

• Mo Kα radiation

• μ = 0.41 mm⁻¹

• T = 293 (2) K

• 0.26 × 0.15 × 0.15 mm

Data collection

• Bruker APEXII CCD area-detector diffractometer

• Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.984, T _max = 0.987

• 13976 measured reflections

• 2373 independent reflections

• 1719 reflections with I > 2σ(I)

• R _int = 0.023

Refinement

• R[F ² > 2σ(F ²)] = 0.057

• wR(F ²) = 0.210

• S = 1.01

• 2373 reflections

• 145 parameters

• H-atom parameters constrained

• Δρ_max = 0.49 e Å⁻³

• Δρ_min = −0.36 e Å⁻³

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: APEX2 and SAINT (Bruker, 2004 ▶); data reduction: SAINT and XPREP (Bruker, 2004 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia (1997 ▶); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2003 ▶).

Supplementary Material

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—H1⋯O1i	0.93	2.47	3.374 (5)	165
C13—H13⋯O1ii	0.93	2.33	3.255 (4)	171
C11—H11⋯Cgiii	0.93	3.12	3.936 (5)	148

Symmetry codes: (i) ; (ii) ; (iii) . Cg is the centroid of the C10/C11/C12/C13/S1 thio­phene ring.

supplementary crystallographic information

Comment

Chalcones with the general formula Ar—CH═CH—CO—Ar are an important class of compounds, with the common structural entity being the central –CH═CH—C(═O)- group, in the H atoms can be substituted. The –C═C– double bond can be photoreactive and can produce various products through solid-state photo cycloaddition. Therefore, chalcones are widely used in organic solid-state photochemistry (Gould et al., 1995). Reviews on the bioactivities of various chalcones have been reported (Go et al., 2005). Bis-chalcones are also found to exhibit good NLO properties (Uchida et al., 1998). In view of this biological importance, the crystal structure of the title compound (I), (1E, 4E)-1,5-Bis(2-thienyl)penta-1,4-dien-3-one (Fig. 1) has been determined and the results are presented here.

Compound (I) consists of two thiophene rings A and B. The central position of (I) shows double and single bonds orientating from O1 atom and five C atom behave like a backbone. The planarities of rings A and B are fairly good. The bond lengths in the (I) are normal and comparable with the corresponding values observed in the related structure (Arshad et al., 2008). The dihedral angle between the two thiophene rings is 14.3 (1)°. The crystal packing (Fig. 2) is stabilized by C—H···π interactions between a thiophene H atom and a neighbouring thiophene ring, with a C11—H11···Cgⁱⁱⁱ separetion of 2.34 Å (Fig. 2 and Table 1; Cg is the centroid of the C10/C11/C12/C13/S1 thiophene ring, symmetry code as in Fig. 2). The molecular packing is further stabilized by intermolecular C—H···O hydrogen bonds (Fig. 2 and Table 1; symmetry code as in Fig. 2).

Experimental

A solution of sodium hydroxide (10 g, 0.25 mol) in water (50 ml) was added to a solution of acetone (5 ml) and 2-thiophenecarboxaldehyde (22.4 g, 0.2 mol) in methanol (50 ml) at 273 K. This mixture was stirred overnight and the product was filtered. Single crystals suitable for X-ray diffraction was obtained by slow evaporation of a solution of the title compound in ethyl acetate.

Refinement

All H atoms were fixed geometrically and allowed to ride on their parent atoms, with N—H=0.86Å and C—H= 0.93–0.98Å with U_iso(H)= 1.5U_eq(methyl H) and 1.2U_eq(for other H atoms).

Figures

Fig. 1.

The molecular structure of title compound showing 30% probability displacement ellipsoids.

Fig. 2.

C—H···π and C—H···O interactions (dotted lines) in the title compound. Cg denotes the ring centroid. [Symmetry code: (i) x-1/2, -y+1/2, -z+1; (ii)x-1/2, y, -z+1/2; (iii) x-1/2, y, -z+1/2; (iv) -x+3/2, y-1/2, z; (v)-x+1, y+1/2, -z+1/2.]

Crystal data

C13H10OS2	F000 = 1024
Mr = 246.35	Dx = 1.332 Mg m−3
Orthorhombic, Pbca	Mo Kα radiation λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 10259 reflections
a = 12.1141 (4) Å	θ = 2.3–30.3º
b = 7.4449 (3) Å	µ = 0.41 mm−1
c = 27.246 (1) Å	T = 293 (2) K
V = 2457.27 (16) Å3	Block, colourless
Z = 8	0.26 × 0.15 × 0.15 mm

Data collection

Bruker APEXII CCD area-detector diffractometer	2373 independent reflections
Radiation source: fine-focus sealed tube	1719 reflections with I > 2σ(I)
Monochromator: graphite	Rint = 0.023
Detector resolution: 10 pixels mm-1	θmax = 26.0º
T = 293(2) K	θmin = 1.5º
ω scans	h = −11→14
Absorption correction: Multi-scan(SADABS; Sheldrick, 1996)	k = −7→9
Tmin = 0.984, Tmax = 0.987	l = −32→31
13976 measured reflections

Refinement

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.057	H-atom parameters constrained
wR(F2) = 0.211	w = 1/[σ2(Fo2) + (0.1295P)2 + 1.4091P] where P = (Fo2 + 2Fc2)/3
S = 1.01	(Δ/σ)max < 0.001
2373 reflections	Δρmax = 0.49 e Å−3
145 parameters	Δρmin = −0.36 e Å−3
Primary atom site location: structure-invariant direct methods	Extinction correction: none

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > 2sigma(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
S1	0.52710 (7)	0.54328 (13)	0.23889 (4)	0.0733 (4)
S2	0.53529 (8)	0.23805 (14)	0.51370 (4)	0.0801 (4)
O1	0.82061 (18)	0.5548 (4)	0.38920 (9)	0.0734 (7)
C1	0.5312 (3)	0.2113 (6)	0.57495 (18)	0.0876 (13)
H1	0.4768	0.1455	0.5910	0.105*
C2	0.6135 (4)	0.2934 (6)	0.59817 (16)	0.0907 (12)
H2	0.6209	0.2904	0.6321	0.109*
C3	0.6903 (3)	0.3874 (5)	0.56716 (12)	0.0667 (9)
H3	0.7525	0.4507	0.5773	0.080*
C4	0.6519 (3)	0.3642 (4)	0.51665 (13)	0.0612 (8)
C5	0.7055 (3)	0.4350 (4)	0.47339 (13)	0.0610 (8)
H5	0.7755	0.4843	0.4774	0.073*
C6	0.6638 (3)	0.4359 (4)	0.42854 (13)	0.0612 (8)
H6	0.5938	0.3881	0.4236	0.073*
C7	0.7236 (2)	0.5093 (4)	0.38617 (12)	0.0573 (8)
C8	0.6611 (2)	0.5283 (4)	0.34019 (12)	0.0594 (8)
H8	0.5901	0.4810	0.3384	0.071*
C9	0.7027 (2)	0.6109 (4)	0.30106 (12)	0.0565 (7)
H9	0.7733	0.6583	0.3045	0.068*
C10	0.6513 (2)	0.6354 (4)	0.25413 (12)	0.0536 (7)
C11	0.6974 (2)	0.7299 (4)	0.21337 (11)	0.0541 (7)
H11	0.7653	0.7882	0.2132	0.065*
C12	0.6228 (3)	0.7207 (6)	0.17301 (14)	0.0794 (10)
H12	0.6364	0.7764	0.1431	0.095*
C13	0.5322 (3)	0.6260 (6)	0.18183 (15)	0.0774 (11)
H13	0.4771	0.6074	0.1586	0.093*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
S1	0.0542 (6)	0.0750 (6)	0.0909 (8)	−0.0090 (4)	−0.0089 (4)	−0.0068 (5)
S2	0.0619 (6)	0.0821 (7)	0.0962 (9)	−0.0065 (4)	0.0047 (4)	0.0076 (5)
O1	0.0483 (13)	0.1008 (18)	0.0710 (16)	−0.0067 (11)	0.0009 (10)	−0.0029 (12)
C1	0.069 (2)	0.090 (3)	0.103 (3)	0.0109 (19)	0.018 (2)	0.033 (2)
C2	0.091 (3)	0.113 (3)	0.068 (2)	0.012 (3)	0.000 (2)	0.013 (2)
C3	0.071 (2)	0.073 (2)	0.056 (2)	−0.0057 (16)	−0.0001 (15)	0.0110 (15)
C4	0.0558 (17)	0.0542 (15)	0.074 (2)	0.0020 (13)	0.0024 (14)	0.0003 (14)
C5	0.0527 (16)	0.0593 (17)	0.071 (2)	−0.0027 (13)	−0.0005 (15)	−0.0028 (14)
C6	0.0510 (16)	0.0621 (17)	0.071 (2)	−0.0018 (13)	0.0012 (14)	−0.0036 (15)
C7	0.0497 (17)	0.0576 (16)	0.065 (2)	0.0021 (13)	0.0033 (13)	−0.0081 (14)
C8	0.0467 (15)	0.0646 (17)	0.067 (2)	−0.0029 (13)	0.0012 (14)	−0.0081 (15)
C9	0.0435 (14)	0.0592 (16)	0.067 (2)	−0.0007 (12)	−0.0031 (13)	−0.0097 (14)
C10	0.0457 (15)	0.0511 (14)	0.0641 (19)	0.0013 (12)	−0.0020 (13)	−0.0103 (13)
C11	0.0442 (14)	0.0624 (17)	0.0558 (18)	−0.0046 (12)	−0.0030 (12)	−0.0082 (13)
C12	0.081 (2)	0.096 (3)	0.062 (2)	0.013 (2)	0.0044 (18)	−0.0026 (18)
C13	0.063 (2)	0.091 (3)	0.078 (3)	0.0085 (18)	−0.0146 (17)	−0.022 (2)

Geometric parameters (Å, °)

S1—C13	1.673 (5)	C6—C7	1.468 (5)
S1—C10	1.704 (3)	C6—H6	0.9300
S2—C1	1.682 (5)	C7—C8	1.471 (5)
S2—C4	1.699 (3)	C8—C9	1.330 (5)
O1—C7	1.225 (4)	C8—H8	0.9300
C1—C2	1.330 (6)	C9—C10	1.434 (4)
C1—H1	0.9300	C9—H9	0.9300
C2—C3	1.438 (5)	C10—C11	1.429 (4)
C2—H2	0.9300	C11—C12	1.425 (5)
C3—C4	1.463 (5)	C11—H11	0.9300
C3—H3	0.9300	C12—C13	1.326 (5)
C4—C5	1.445 (5)	C12—H12	0.9300
C5—C6	1.322 (5)	C13—H13	0.9300
C5—H5	0.9300
C13—S1—C10	92.62 (17)	O1—C7—C8	121.6 (3)
C1—S2—C4	92.5 (2)	C6—C7—C8	116.8 (3)
C2—C1—S2	113.3 (3)	C9—C8—C7	122.1 (3)
C2—C1—H1	123.3	C9—C8—H8	118.9
S2—C1—H1	123.3	C7—C8—H8	118.9
C1—C2—C3	115.4 (4)	C8—C9—C10	127.5 (3)
C1—C2—H2	122.3	C8—C9—H9	116.3
C3—C2—H2	122.3	C10—C9—H9	116.3
C2—C3—C4	106.8 (3)	C9—C10—C11	125.9 (3)
C2—C3—H3	126.6	C9—C10—S1	123.3 (2)
C4—C3—H3	126.6	C11—C10—S1	110.7 (2)
C5—C4—C3	125.6 (3)	C12—C11—C10	109.1 (3)
C5—C4—S2	122.5 (3)	C12—C11—H11	125.4
C3—C4—S2	112.0 (2)	C10—C11—H11	125.4
C6—C5—C4	125.7 (3)	C13—C12—C11	114.2 (4)
C6—C5—H5	117.1	C13—C12—H12	122.9
C4—C5—H5	117.1	C11—C12—H12	122.9
C5—C6—C7	122.7 (3)	C12—C13—S1	113.3 (3)
C5—C6—H6	118.7	C12—C13—H13	123.4
C7—C6—H6	118.7	S1—C13—H13	123.4
O1—C7—C6	121.5 (3)
C4—S2—C1—C2	0.3 (4)	O1—C7—C8—C9	−6.5 (5)
S2—C1—C2—C3	−0.5 (5)	C6—C7—C8—C9	172.5 (3)
C1—C2—C3—C4	0.5 (5)	C7—C8—C9—C10	178.8 (3)
C2—C3—C4—C5	−179.2 (3)	C8—C9—C10—C11	177.9 (3)
C2—C3—C4—S2	−0.3 (4)	C8—C9—C10—S1	−5.4 (4)
C1—S2—C4—C5	179.0 (3)	C13—S1—C10—C9	−177.9 (3)
C1—S2—C4—C3	0.1 (3)	C13—S1—C10—C11	−0.8 (2)
C3—C4—C5—C6	−170.2 (3)	C9—C10—C11—C12	178.5 (3)
S2—C4—C5—C6	11.1 (5)	S1—C10—C11—C12	1.5 (3)
C4—C5—C6—C7	−179.5 (3)	C10—C11—C12—C13	−1.6 (4)
C5—C6—C7—O1	8.6 (5)	C11—C12—C13—S1	1.0 (4)
C5—C6—C7—C8	−170.4 (3)	C10—S1—C13—C12	−0.1 (3)

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···O1i	0.93	2.47	3.374 (5)	165
C13—H13···O1ii	0.93	2.33	3.255 (4)	171
C11—H11···Cgiii	0.93	3.12	3.936 (5)	148

Symmetry codes: (i) x−1/2, −y+1/2, −z+1; (ii) x−1/2, y, −z+1/2; (iii) −x+3/2, y+1/2, z.