(Z)-2-(2-Chloro-3,3,3-trifluoro­prop-1-en­yl)-6-methoxy­phenyl acetate

Hua Zhou; Zhi-Gang Li; Jing-Wei Xu

doi:10.1107/S160053680801489X

. 2008 May 30;64(Pt 6):o1166. doi: 10.1107/S160053680801489X

(Z)-2-(2-Chloro-3,3,3-trifluoroprop-1-enyl)-6-methoxyphenyl acetate

Hua Zhou ^a, Zhi-Gang Li ^a, Jing-Wei Xu ^a,^*

PMCID: PMC2961540 PMID: 21202673

Abstract

The crystal structure of the title compound, C₁₂H₁₀ClF₃O₃, was determined in order to establish the configuration of the C=double bond. The compound was found to be the Z isomer. The crystal structure is dominated by Cl⋯O halogen bonds [Cl⋯O = 3.111 (3) Å], as well as C—H⋯O and C—H⋯F hydrogen-bonding interactions, that connect neighboring molecules into a three-dimensional supramolecular network.

Related literature

For related literature, see: Dmowski (1985 ▶); Fujita & Hiyama (1986 ▶); Nenajdenko et al.(2005 ▶); Politzer et al. (2007 ▶).

Experimental

Crystal data

C₁₂H₁₀ClF₃O₃
M _r = 294.65
Triclinic,
a = 8.6168 (19) Å
b = 8.6850 (19) Å
c = 9.723 (2) Å
α = 77.323 (3)°
β = 70.869 (3)°
γ = 84.010 (3)°
V = 670.3 (3) Å³
Z = 2
Mo Kα radiation
μ = 0.32 mm⁻¹
T = 293 (2) K
0.16 × 0.10 × 0.09 mm

Data collection

Bruker APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.943, T _max = 0.968
3677 measured reflections
2551 independent reflections
1967 reflections with I > 2σ(I)
R _int = 0.009

Refinement

R[F ² > 2σ(F ²)] = 0.052
wR(F ²) = 0.146
S = 1.03
2551 reflections
174 parameters
H-atom parameters constrained
Δρ_max = 0.31 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Data collection: SMART (Bruker, 1998 ▶); cell refinement: SAINT-Plus (Bruker, 2003 ▶); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053680801489X/zl2108sup1.cif

e-64-o1166-sup1.cif^{(16KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S160053680801489X/zl2108Isup2.hkl

e-64-o1166-Isup2.hkl^{(125.3KB, 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
C6—H6⋯F1ⁱ	0.93	2.64	3.508 (3)	156
C7—H7⋯O2ⁱⁱ	0.93	2.60	3.430 (3)	149

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

Acknowledgments

This work was supported by Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, People’s Republic of China.

supplementary crystallographic information

Comment

The title compound is an intermediate in the synthesis of trifluoromethyl substituted benzofurans. The configuration of analogue compounds such as 2-fluoro-3,3,3-trifluoroprop-1-enes (Dmowski, 1985), 2-chloro-3,3,3-trifluoroprop-1-enes (Fujita & Hiyama, 1986) or 2-bromo-3,3,3-trifluoroprop-1-enes (Nenajdenko et al., 2005) were determined by ¹H and ¹⁹F NMR. The configuration of the title compound, however, could not be determined with enough confidence by ¹H and ¹⁹F NMR due to lack of data such as hetero-nuclear coupling constants, and its crystal structure was determined instead to determine its configuiration.

As shown in Fig. 1, the title compound is the Z isomer with the phenyl ring and the Cl atom on the same side of the C═C double bond. The C═C double bond and the ester bond have a large torsional angle with the phenyl ring with a tilting angle of the double bond and a dihedral angle between the planes of the ester and the phenyl ring of 66.01 (4)° and 83.15 (3)°, respectively. The ether bond, on the other hand, is nearly coplanar with the the phenyl ring, with a dihedral angle between the normal of the phenyl ring plane and the ether bond of 87.34 (3)°.

The molecular packing is stablized by Cl···O halogen bonds (Politzer et al., 2007) between the Cl atom and the oxygen of a neighbouring ether bond, with a Cl—O3ⁱ distance of 3.111 (3) Å (symmetry code as in Fig. 2) and a nearly linear C—Cl···O3ⁱ angle of 178.0 (2)°. In addition, intermolecular C—H···O and C—H···F hydrogen bonds are present (Table 1 and Fig. 2). The two kinds of interactions lead to a three-dimensional supramolecular network. (Fig. 2).

Experimental

The title compound was synthesized by a modified literature procedure (Fujita & Hiyama, 1986). Zinc powder (3.25 g, 50 mmol) and acetic anhydride (3.06 g, 30 mmol) were added into a solution of 2-hydroxy-3-methoxybenzaldehyde (1.52 g,10 mmol) in DMF (20 ml, dried by 4Å molecular sieve) under an argon atmosphere at room temperature. Then 1,1,1-trichloro-2,2,2-trifluoroethane (5.63 g, 30 mmol) was added dropwise to the mixture over ten minutes with fierce stirring. The reaction was monitored by thin layer chromatography. After completion, the reaction mixture was treated with saturated aqueous ammonium chloride solution (150 ml), and extracted with diethyl ether (3 × 50 ml). The organic phase was dried with magnesium sulfate, concentrated, and purification by silica gel column chromatography using petroleum ether as the eluent (R_f = 0.15). The purified product was recrystallized from petroleum ether to obtain colorless platelike crystals (1.47 g, 50%).