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

Caracelli, I.; Maganhi, S.H.; Stefani, H.A.; Gueogjian, K.; Tiekink, E.R.T.

doi:10.1107/S2056989015002157

organic compounds

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Volume 71| Part 3| March 2015| Pages o154-o155

doi:10.1107/S2056989015002157

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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 and Edward R. T. Tiekink ^c

^aDepartmento de Física, Universidade Federal de São Carlos, 13565-905 São Carlos, SP, Brazil, ^bDepartamento de Farmácia, Faculdade de Ciências Farmacêuticas, Universidade de São Paulo, 05508-900 São Paulo, SP, Brazil, and ^cDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: ignez@ufscar.br

Edited by H. Stoeckli-Evans, University of Neuchâtel, Switzerland (Received 26 January 2015; accepted 2 February 2015; online 7 February 2015)

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.

CCDC reference: 1046686

1. 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 ).

2. Experimental

2.1. Crystal data

C₁₅H₈O₂S
M_r = 252.27
Monoclinic, P 2₁ /c
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

2.2. 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

2.3. Refinement

R[F² > 2σ(F²)] = 0.050
wR(F²) = 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

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of ring S1,C1⋯C4.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C14—H14⋯Cg1ⁱ	0.95	2.89	3.701 (2)	144
Symmetry code: (i) $[x-1, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

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 ).

Supporting information

CCDC reference: 1046686

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: 10.1107/S2056989015002157/su5073sup1.cif

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

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

checkCIF report

Synthesis and crystallization top

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.

Refinement top

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).

Comment top

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).

Related literature top

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).

Experimental top

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.

Computing details top

Data collection: CrysAlis PRO (Agilent, 2011); cell refinement: CrysAlis PRO (Agilent, 2011); data reduction: CrysAlis PRO (Agilent, 2011); 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).

Figures top

	Fig. 1. Molecular structure of the title compound showing atom labelling and displacement ellipsoids at the 70% probability level.
	Fig. 2. 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.

3-[2-(Thiophen-3-yl)ethynyl]-2H-chromen-2-one top

Crystal data top

C₁₅H₈O₂S	F(000) = 520
M_r = 252.27	D_x = 1.447 Mg m⁻³
Monoclinic, P2₁/c	Cu Kα radiation, λ = 1.54184 Å
a = 10.7726 (6) Å	Cell parameters from 2362 reflections
b = 9.7572 (3) Å	θ = 4.0–76.0°
c = 12.2084 (5) Å	µ = 2.40 mm⁻¹
β = 115.547 (6)°	T = 100 K
V = 1157.77 (11) Å³	Prism, dark yellow
Z = 4	0.25 × 0.15 × 0.05 mm

Data collection top

Agilent CCD diffractometer	2108 reflections with I > 2σ(I)
Radiation source: SuperNova (Cu) X-ray Source	R_int = 0.023
ω scans	θ_max = 76.2°, θ_min = 4.6°
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	h = −13→11
T_min = 0.338, T_max = 1.000	k = −12→10
4511 measured reflections	l = −15→14
2373 independent reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.050	H-atom parameters constrained
wR(F²) = 0.156	w = 1/[σ²(F_o²) + (0.1031P)² + 0.5663P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max < 0.001
2373 reflections	Δρ_max = 0.42 e Å⁻³
163 parameters	Δρ_min = −0.57 e Å⁻³
0 restraints

Crystal data top

C₁₅H₈O₂S	V = 1157.77 (11) Å³
M_r = 252.27	Z = 4
Monoclinic, P2₁/c	Cu Kα radiation
a = 10.7726 (6) Å	µ = 2.40 mm⁻¹
b = 9.7572 (3) Å	T = 100 K
c = 12.2084 (5) Å	0.25 × 0.15 × 0.05 mm
β = 115.547 (6)°

Data collection top

Agilent CCD diffractometer	2373 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	2108 reflections with I > 2σ(I)
T_min = 0.338, T_max = 1.000	R_int = 0.023
4511 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.050	0 restraints
wR(F²) = 0.156	H-atom parameters constrained
S = 1.06	Δρ_max = 0.42 e Å⁻³
2373 reflections	Δρ_min = −0.57 e Å⁻³
163 parameters

Special details top

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

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
S1	1.08150 (6)	0.79946 (6)	0.56811 (5)	0.0338 (2)
O1	0.47823 (14)	0.23152 (14)	0.60599 (12)	0.0194 (3)
O2	0.62583 (14)	0.39103 (15)	0.71228 (12)	0.0236 (3)
C1	1.0505 (2)	0.80962 (19)	0.69506 (19)	0.0225 (4)
H1	1.0976	0.8684	0.7624	0.027*
C2	0.9466 (2)	0.7191 (2)	0.68413 (19)	0.0236 (4)
H2	0.9143	0.7081	0.7448	0.028*
C3	0.8928 (2)	0.64361 (19)	0.57262 (18)	0.0204 (4)
C4	0.9581 (2)	0.6785 (2)	0.50099 (19)	0.0274 (5)
H4	0.9368	0.6396	0.4236	0.033*
C5	0.7859 (2)	0.5442 (2)	0.54250 (17)	0.0207 (4)
C6	0.69803 (19)	0.4614 (2)	0.52352 (16)	0.0198 (4)
C11	0.57073 (19)	0.3326 (2)	0.61608 (17)	0.0186 (4)
C7	0.59579 (19)	0.35987 (19)	0.50841 (17)	0.0183 (4)
C8	0.5239 (2)	0.29061 (19)	0.40315 (18)	0.0194 (4)
H8	0.5380	0.3115	0.3334	0.023*
C9	0.4272 (2)	0.18649 (19)	0.39642 (18)	0.0183 (4)
C15	0.3539 (2)	0.1072 (2)	0.29190 (17)	0.0211 (4)
H15	0.3642	0.1249	0.2198	0.025*
C14	0.2672 (2)	0.00402 (19)	0.29346 (18)	0.0216 (4)
H14	0.2187	−0.0497	0.2229	0.026*
C13	0.2510 (2)	−0.0214 (2)	0.39989 (18)	0.0224 (4)
H13	0.1905	−0.0920	0.4004	0.027*
C12	0.3219 (2)	0.0550 (2)	0.50393 (18)	0.0218 (4)
H12	0.3114	0.0371	0.5759	0.026*
C10	0.40856 (19)	0.1581 (2)	0.50072 (17)	0.0185 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0356 (4)	0.0357 (4)	0.0303 (4)	−0.0118 (2)	0.0144 (3)	0.0005 (2)
O1	0.0231 (7)	0.0234 (7)	0.0148 (6)	−0.0009 (5)	0.0109 (5)	0.0002 (5)
O2	0.0262 (7)	0.0299 (8)	0.0159 (7)	−0.0019 (6)	0.0102 (6)	−0.0023 (6)
C1	0.0212 (9)	0.0219 (9)	0.0222 (10)	0.0033 (7)	0.0072 (8)	−0.0011 (7)
C2	0.0254 (10)	0.0257 (9)	0.0209 (10)	0.0022 (8)	0.0112 (8)	−0.0019 (7)
C3	0.0221 (9)	0.0205 (9)	0.0182 (9)	0.0010 (7)	0.0082 (7)	0.0021 (7)
C4	0.0334 (11)	0.0304 (10)	0.0194 (10)	−0.0080 (9)	0.0122 (9)	−0.0008 (8)
C5	0.0244 (9)	0.0241 (9)	0.0154 (8)	0.0034 (8)	0.0104 (7)	0.0018 (7)
C6	0.0246 (10)	0.0218 (9)	0.0142 (8)	0.0040 (7)	0.0096 (7)	0.0005 (7)
C11	0.0211 (9)	0.0202 (9)	0.0159 (9)	0.0030 (7)	0.0092 (7)	0.0009 (7)
C7	0.0208 (9)	0.0197 (9)	0.0164 (9)	0.0016 (7)	0.0099 (7)	0.0016 (7)
C8	0.0228 (9)	0.0226 (9)	0.0160 (9)	0.0000 (7)	0.0113 (8)	0.0006 (7)
C9	0.0207 (9)	0.0183 (8)	0.0174 (9)	0.0011 (7)	0.0098 (7)	0.0002 (7)
C15	0.0245 (9)	0.0255 (9)	0.0146 (8)	0.0006 (7)	0.0097 (7)	−0.0003 (7)
C14	0.0238 (9)	0.0213 (9)	0.0194 (9)	0.0002 (7)	0.0092 (7)	−0.0020 (7)
C13	0.0227 (9)	0.0230 (9)	0.0224 (10)	−0.0020 (7)	0.0105 (8)	0.0014 (7)
C12	0.0255 (10)	0.0235 (9)	0.0198 (9)	0.0026 (8)	0.0130 (8)	0.0048 (7)
C10	0.0210 (9)	0.0200 (9)	0.0148 (9)	0.0019 (7)	0.0081 (7)	−0.0008 (7)

Geometric parameters (Å, º) top

S1—C4	1.701 (2)	C11—C7	1.476 (3)
S1—C1	1.723 (2)	C7—C8	1.360 (3)
O1—C11	1.369 (2)	C8—C9	1.432 (3)
O1—C10	1.377 (2)	C8—H8	0.9500
O2—C11	1.206 (2)	C9—C10	1.400 (3)
C1—C2	1.387 (3)	C9—C15	1.408 (3)
C1—H1	0.9500	C15—C14	1.378 (3)
C2—C3	1.432 (3)	C15—H15	0.9500
C2—H2	0.9500	C14—C13	1.406 (3)
C3—C4	1.381 (3)	C14—H14	0.9500
C3—C5	1.426 (3)	C13—C12	1.384 (3)
C4—H4	0.9500	C13—H13	0.9500
C5—C6	1.189 (3)	C12—C10	1.384 (3)
C6—C7	1.433 (3)	C12—H12	0.9500

C4—S1—C1	93.39 (10)	C7—C8—C9	120.69 (18)
C11—O1—C10	122.76 (15)	C7—C8—H8	119.7
C2—C1—S1	109.76 (15)	C9—C8—H8	119.7
C2—C1—H1	125.1	C10—C9—C15	118.13 (18)
S1—C1—H1	125.1	C10—C9—C8	118.32 (18)
C1—C2—C3	113.49 (19)	C15—C9—C8	123.50 (18)
C1—C2—H2	123.3	C14—C15—C9	120.50 (17)
C3—C2—H2	123.3	C14—C15—H15	119.8
C4—C3—C5	125.39 (18)	C9—C15—H15	119.8
C4—C3—C2	111.53 (18)	C15—C14—C13	119.78 (18)
C5—C3—C2	123.08 (18)	C15—C14—H14	120.1
C3—C4—S1	111.83 (16)	C13—C14—H14	120.1
C3—C4—H4	124.1	C12—C13—C14	120.90 (18)
S1—C4—H4	124.1	C12—C13—H13	119.6
C6—C5—C3	176.60 (19)	C14—C13—H13	119.6
C5—C6—C7	176.52 (19)	C13—C12—C10	118.53 (17)
O2—C11—O1	117.48 (17)	C13—C12—H12	120.7
O2—C11—C7	125.43 (18)	C10—C12—H12	120.7
O1—C11—C7	117.09 (16)	O1—C10—C12	117.02 (16)
C8—C7—C6	123.92 (17)	O1—C10—C9	120.80 (17)
C8—C7—C11	120.25 (17)	C12—C10—C9	122.17 (18)
C6—C7—C11	115.83 (16)

C4—S1—C1—C2	0.47 (17)	C7—C8—C9—C10	0.1 (3)
S1—C1—C2—C3	−0.5 (2)	C7—C8—C9—C15	−177.24 (18)
C1—C2—C3—C4	0.3 (3)	C10—C9—C15—C14	−0.5 (3)
C1—C2—C3—C5	179.59 (18)	C8—C9—C15—C14	176.84 (18)
C5—C3—C4—S1	−179.21 (16)	C9—C15—C14—C13	0.6 (3)
C2—C3—C4—S1	0.1 (2)	C15—C14—C13—C12	−0.6 (3)
C1—S1—C4—C3	−0.30 (18)	C14—C13—C12—C10	0.5 (3)
C10—O1—C11—O2	179.74 (16)	C11—O1—C10—C12	177.52 (16)
C10—O1—C11—C7	−0.9 (3)	C11—O1—C10—C9	−1.6 (3)
O2—C11—C7—C8	−177.71 (19)	C13—C12—C10—O1	−179.57 (16)
O1—C11—C7—C8	3.0 (3)	C13—C12—C10—C9	−0.5 (3)
O2—C11—C7—C6	2.3 (3)	C15—C9—C10—O1	179.50 (16)
O1—C11—C7—C6	−177.02 (15)	C8—C9—C10—O1	2.0 (3)
C6—C7—C8—C9	177.45 (17)	C15—C9—C10—C12	0.5 (3)
C11—C7—C8—C9	−2.6 (3)	C8—C9—C10—C12	−177.01 (17)

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of ring S1,C1···C4.

D—H···A	D—H	H···A	D···A	D—H···A
C14—H14···Cg1ⁱ	0.95	2.89	3.701 (2)	144

Symmetry code: (i) x−1, −y+1/2, z−1/2.

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of ring S1,C1···C4.

D—H···A	D—H	H···A	D···A	D—H···A
C14—H14···Cg1ⁱ	0.95	2.89	3.701 (2)	144

Symmetry code: (i) x−1, −y+1/2, z−1/2.

Acknowledgements

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.

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