Crystal structure of 3-[2-(thio­phen-3-yl)ethyn­yl]-2H-chromen-2-one

Ignez Caracelli; Stella H Maganhi; Hélio A Stefani; Karina Gueogjian; Edward R T Tiekink

doi:10.1107/S2056989015002157

. 2015 Feb 7;71(Pt 3):o154–o155. doi: 10.1107/S2056989015002157

Crystal structure of 3-[2-(thiophen-3-yl)ethynyl]-2H-chromen-2-one

Ignez Caracelli ^a,^*, Stella H Maganhi ^a, Hélio A Stefani ^b, Karina Gueogjian ^b, Edward R T Tiekink ^c

PMCID: PMC4350713 PMID: 25844223

Abstract

In the title compound, C₁₅H₈O₂S, the coumarin moiety is approximately planar (r.m.s. deviation of the 11 non-H atoms = 0.025 Å) and is slightly inclined with respect to the plane of the thiophen-3-yl ring, forming a dihedral angle of 11.75 (8)°. In the crystal, the three-dimensional architecture features a combination of coumarin–thiophene C—H⋯π and π–π [inter-centroid distance = 3.6612 (12) Å] interactions.

Keywords: crystal structure, coumarin, asymmetric alkyne, C—H⋯π interactions, π–π interactions

Related literature

For the wide range of different biological activities of coumarins, see: Wu et al. (2009 ▸); Roussaki et al. (2014 ▸). For background to our ongoing interest in the synthesis and crystal structures of coumarin derivatives, see: Stefani et al. (2012 ▸); Caracelli et al. (2015 ▸). For the synthesis of the title compound, see: Gueogjian (2011 ▸). graphic file with name e-71-0o154-scheme1.jpg

Experimental

Crystal data

C₁₅H₈O₂S
M _r = 252.27
Monoclinic,
a = 10.7726 (6) Å
b = 9.7572 (3) Å
c = 12.2084 (5) Å
β = 115.547 (6)°
V = 1157.77 (11) Å³
Z = 4
Cu Kα radiation
μ = 2.40 mm⁻¹
T = 100 K
0.25 × 0.15 × 0.05 mm

Data collection

Agilent CCD diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011 ▸) T _min = 0.338, T _max = 1.000
4511 measured reflections
2373 independent reflections
2108 reflections with I > 2σ(I)
R _int = 0.023

Refinement

R[F ² > 2σ(F ²)] = 0.050
wR(F ²) = 0.156
S = 1.06
2373 reflections
163 parameters
H-atom parameters constrained
Δρ_max = 0.42 e Å⁻³
Δρ_min = −0.57 e Å⁻³

Data collection: CrysAlis PRO (Agilent, 2011 ▸); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SIR2014 (Burla et al., 2015 ▸); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015 ▸); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▸) and DIAMOND (Brandenburg, 2006 ▸); software used to prepare material for publication: MarvinSketch (ChemAxon, 2010 ▸) and publCIF (Westrip, 2010 ▸).

Supplementary Material

Crystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S2056989015002157/su5073sup1.cif

e-71-0o154-sup1.cif^{(171.4KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015002157/su5073Isup2.hkl

e-71-0o154-Isup2.hkl^{(130.5KB, hkl)}

Click here for additional data file.^{(4.4KB, cml)}

Supporting information file. DOI: 10.1107/S2056989015002157/su5073Isup3.cml

Click here for additional data file.^{(1,021.4KB, tif)}

. DOI: 10.1107/S2056989015002157/su5073fig1.tif

Molecular structure of the title compound showing atom labelling and displacement ellipsoids at the 70% probability level.

Click here for additional data file.^{(1.6MB, tif)}

b . DOI: 10.1107/S2056989015002157/su5073fig2.tif

A view in projection down the b axis of the unit-cell contents. The π–π and C—H⋯π interactions are shown as purple and orange dashed lines, respectively.

CCDC reference: 1046686

Additional supporting information: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (, ).

Cg1 is the centroid of ring S1,C1C4.

DHA	DH	HA	D A	DHA
C14H14Cg1ⁱ	0.95	2.89	3.701(2)	144

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Symmetry code: (i) Inline graphic .

Acknowledgments

The Brazilian agencies CNPq (306121/2013–2 to IC and 308320/2010–7 to HAS), FAPESP (2012/00424–2) and CAPES are acknowledged for financial support.

supplementary crystallographic information

S1. Synthesis and crystallization

The title compound was prepared as per Gueogjian (2011). 3-Bromo coumarin (112.5 mg, 0.5 mmol), potassium trifluoroborate salt (0.55 mmol), PdCl₂ (dppf).CH₂Cl₂ (41 mg, 10 mol%),i-Pr₂NEt (0.3 mL, 1.5 mmol) and 1,4-dioxane/H₂O (2/1, 3 mL), in acetonitrile (20 mL) were added to a two-necked round-bottomed flask equipped with a reflux condenser under N₂. The reaction mixture was heated under reflux at 353 K, and was monitored by TLC and GC analysis. After the consumption of the 3-bromocoumarin, the mixture was extracted twice with ethyl acetate (50 mL). The organic phase was separated, dried over MgSO₄ and concentrated under vacuum. The residue was purified by flash chromatography (ethyl acetate/hexane 10:90). The title compound was obtained as a dark-yellow solid in 53% yield. Suitable crystals were obtained by slow evaporation from a mixture of ethyl acetate/hexane.

S2. Refinement

C-bound H-atoms were placed in calculated positions (C—H = 0.95 Å) and were included in the refinement in the riding model approximation, with U_iso(H) = 1.2U_eq(C).

S3. Comment

Coumarins are heterocycles presenting a wide range of different biological activities (Wu et al., 2009; Roussaki et al., 2014). As part of our on-going interest in the synthesis and crystal structures of coumarin derivatives with biological activity (Stefani et al., 2012; Caracelli et al., 2015) the title compound was synthesized (Gueogjian, 2011).

S4. Experimental

The title compound was prepared as per Gueogjian (2011). 3-Bromo coumarin (112.5 mg, 0.5 mmol), potassium trifluoroborate salt (0.55 mmol), PdCl₂ (dppf)·CH₂Cl₂ (41 mg, 10 mol%),i-Pr₂NEt (0.3 ml, 1.5 mmol) and 1,4-dioxane/H₂O (2/1, 3 ml), in acetonitrile (20 ml) were added to a two-necked round-bottomed flask equipped with a reflux condenser under N₂. The reaction mixture was heated under reflux at 353 K, and was monitored by TLC and GC analysis. After the consumption of the 3-bromocoumarin, the mixture was extracted twice with ethyl acetate (50 ml). The organic phase was separated, dried over MgSO₄ and concentrated under vacuum. The residue was purified by flash chromatography (ethyl acetate/hexane 10:90). The title compound was obtained as a dark-yellow solid in 53% yield. Suitable crystals were obtained by slow evaporation from a mixture of ethyl acetate/hexane.