1-{5-[2-Chloro-5-(trifluoro­meth­yl)phen­yl]thio­phen-2-yl}ethanone

Roman Lytvyn; Yuri Horak; Vasyl Matiychuk; Mykola Obushak; Vasyl Kinzhybalo

doi:10.1107/S1600536811003965

. 2011 Feb 9;67(Pt 3):o585. doi: 10.1107/S1600536811003965

1-{5-[2-Chloro-5-(trifluoromethyl)phenyl]thiophen-2-yl}ethanone

Roman Lytvyn ^a, Yuri Horak ^a,^*, Vasyl Matiychuk ^a, Mykola Obushak ^a, Vasyl Kinzhybalo ^b

PMCID: PMC3052071 PMID: 21522346

Abstract

In the title molecule, C₁₃H₈ClF₃OS, the dihedral angle between the mean planes of 2-chloro-5-(trifluoromethyl)phenyl and tiophene rings is 54.37 (5)°. The acethyl group is twisted by 8.1 (2)° with respect to the thiophene ring. The CF₃ group is disordered over two sets of sites with occupations of 0.49 (3) and 0.51 (3). The crystal packing features C—H⋯F and C—H⋯O hydrogen bonds, forming dimers which are connected into chains along the c axis by C—H⋯O hydrogen bonds and C—Cl⋯π [Cl⋯π = 3.415 (1) Å and C—Cl⋯π = 151.56 (5)°] interactions. The chains are further connected into layers perpendicular to the a axis by C—H⋯O interactions.

Related literature

For the general synthetic procedure, see: Matiychuk et al. (2010 ▶). For the biologial activity of arylthiophenes, see: Reddy et al. (2005 ▶); Anderson et al. (1963 ▶); Bohlmann et al. (1984 ▶); Michaelides et al. (1997 ▶); Tanaka et al. (1998 ▶) and for their applications, see Masui et al. (2004 ▶); Roncali (1992 ▶, 1997 ▶). For methods of obtaining arylthiophenes via cross-coupling reactions, see: Stanforth (1998 ▶).

Experimental

Crystal data

C₁₃H₈ClF₃OS
M _r = 304.70
Monoclinic,
a = 15.330 (6) Å
b = 10.809 (4) Å
c = 7.676 (3) Å
β = 93.72 (3)°
V = 1269.3 (8) Å³
Z = 4
Mo Kα radiation
μ = 0.49 mm⁻¹
T = 100 K
0.20 × 0.15 × 0.08 mm

Data collection

Kuma KM-4-CCD diffractometer
Absorption correction: analytical (CrysAlis RED; Oxford Diffraction, 2006 ▶) T _min = 0.86, T _max = 0.93
16021 measured reflections
4377 independent reflections
3093 reflections with I > 2σ(I)
R _int = 0.034

Refinement

R[F ² > 2σ(F ²)] = 0.039
wR(F ²) = 0.097
S = 1.00
4377 reflections
201 parameters
H-atom parameters constrained
Δρ_max = 0.49 e Å⁻³
Δρ_min = −0.25 e Å⁻³

Data collection: CrysAlis CCD (Oxford Diffraction, 2006 ▶); cell refinement: CrysAlis RED (Oxford Diffraction, 2006 ▶); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg, 2006) ▶; software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811003965/ds2088sup1.cif

e-67-0o585-sup1.cif^{(16.5KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811003965/ds2088Isup2.hkl

e-67-0o585-Isup2.hkl^{(214.4KB, hkl)}

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
C22—H22C⋯F1Aⁱ	0.98	2.55	3.520 (13)	168
C22—H22B⋯O1ⁱⁱ	0.98	2.62	3.526 (2)	154
C22—H22A⋯O1ⁱⁱⁱ	0.98	2.67	3.562 (3)	152
C56—H56⋯O1ⁱ	0.95	2.78	3.697 (2)	162

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

Acknowledgments

The authors acknowledge Professor T. Lis (University of Wroclaw) for providing the X-ray data collection faciltities.

supplementary crystallographic information

Comment

Arylthiophenes and their homologues are an important class of organic compounds. The arylthiophenes units are represented in several types of compounds of current interest including polymers (Roncali, 1992; Roncali, 1997), liquid crystals (Masui et al., 2004), ligands and molecules of medicinal interest (Michaelides et al., 1997; Tanaka et al., 1998; Reddy et al., 2005; Anderson et al., 1963). In view of the arylthiophenes importance a number of catalytic methods of these compounds formation from precursors in a cross-coupling reactions have been developed over the last two decades (Stanforth, 1998). However, these methods proceed in two steps via an organometallic intermediate and their stability is often limited.

The molecule of the title compound is not plannar (see Fig. 1). The dihedral angle between the mean planes of 2-chloro-5-(trifluoromethyl)phenyl and tiophene rings is equal to 54.37 (5)°. The acethyl group is twisted with respect to the tiophene ring by 8.1 (2)°. The CF₃ group is disordered with almoust equal occupations of two positions, which are realised by the rotation around C1–C55 bond. The crystal structure packing is governed by the hydrogen bonds of C–H···F and C–H···O types and C–Cl···π interactions. The centrosymmetric dimers are formed by the pairs of C22–H22C···F1Aⁱ and C56–H56···O1ⁱ hydrogen bonds. The dimers are connected into the chains that propagate along z axis direction by means of C22–H22A···O1ⁱⁱⁱ hydrogen bonds and C52–Cl1···C_g^iv interactions (symmetry code: (iv) x, 1/2 - y, z + 1/2). The geometrical parameters of C52–Cl1···C_g^iv interaction are as follows: Cl1···C_g^iv distance is equal to 3.415 (1) Å and the C52–Cl1···C_g^iv angle 151.56 (5)°. The vast layers perpendicular to x axis direction are formed of above mentioned chains connected with each other by C22–H22B···O1ⁱⁱ hydrogen bonds (see Fig. 2).

Experimental

Water solution of 7 g of NaNO₂ (25 ml) was added dropwise to a cooled stirred mixture of 2-chloro-5-trifluoromethylaniline (19.5 g, 0.1 mol, Fluka) and 60 ml of 20% HCl. After completion of reaction the solution was filtered and added dropwise to well stirred mixture of 2-acetylthiophene (12.6 g, 0.1 mol, Fluka), acetone (40 ml) and CuCl₂^.2H₂O (1.5 g, 8.7 mmol) during 20 min. After 3 h the reaction mixture was diluted with 250 ml of water and 50 ml of CHCl₃, organic layer was separated and dried over Na₂SO₄, and concentrated under reduced pressure. Residue was distilled at 400 Pa (453–458 K) and gave 11.6 g (38% yield) of 1-{5-[2-chloro-5-(trifluoromethyl)phenyl]-2-thienyl}ethanone. Yellow crystals suitable for X-ray analysis were obtained by recrystallization from n-hexane.