4-(2-Fluoro­benzo­yl)-1-[2-(4-hy­droxy­phen­yl)-2-oxoeth­yl]piperazin-1-ium trifluoro­acetate

Fuyong Bian; Yi Jin; Shaoming Chi; Guojun Shi; Sichuan Xu

doi:10.1107/S1600536812042857

. 2012 Oct 31;68(Pt 11):o3243. doi: 10.1107/S1600536812042857

4-(2-Fluorobenzoyl)-1-[2-(4-hydroxyphenyl)-2-oxoethyl]piperazin-1-ium trifluoroacetate

Fuyong Bian ^a, Yi Jin ^a, Shaoming Chi ^a, Guojun Shi ^a, Sichuan Xu ^a,^*

PMCID: PMC3515321 PMID: 23284541

Abstract

In the crystal structure of the title compound, C₁₉H₂₀FN₂O₃ ⁺·C₂F₃O₂ ⁻, N—H⋯O and O—H⋯O hydrogen bonds link two cations and two anions into a 22-atom ring. These rings are further linked into a three dimensional network by weak C—H⋯O contacts.

Related literature

For the preparation for the title compound, see: Hoff et al. (2005 ▶); Wallén et al. (2003 ▶); Stachulski et al. (2006 ▶). For similar structures, see: Luedtkea & Mach (2003 ▶); Rok et al. (2007 ▶); Friedel & Crafts (1932a ▶,b ▶). For the applications of similar compounds, see: Wise (1996 ▶).

Experimental

Crystal data

C₁₉H₂₀FN₂O₃ ⁺·C₂F₃O₂ ⁻
M _r = 456.39
Monoclinic,
a = 10.055 (3) Å
b = 9.601 (2) Å
c = 21.946 (5) Å
β = 91.960 (4)°
V = 2117.4 (9) Å³
Z = 4
Mo Kα radiation
μ = 0.13 mm⁻¹
T = 298 K
0.23 × 0.20 × 0.18 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ▶) T _min = 0.956, T _max = 0.971
12540 measured reflections
3824 independent reflections
1534 reflections with I > 2σ(I)
R _int = 0.070

Refinement

R[F ² > 2σ(F ²)] = 0.073
wR(F ²) = 0.240
S = 1.03
3824 reflections
289 parameters
H-atom parameters constrained
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT (Bruker, 2001 ▶); data reduction: SAINT; 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

Click here for additional data file.^{(21.2KB, cif)}

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812042857/qm2083sup1.cif

e-68-o3243-sup1.cif^{(21.2KB, cif)}

Click here for additional data file.^{(201.4KB, hkl)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812042857/qm2083Isup2.hkl

e-68-o3243-Isup2.hkl^{(201.4KB, 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
N1—H1N⋯O5ⁱ	0.91	1.87	2.710 (5)	152
O1—H1⋯O5ⁱⁱ	0.82	1.95	2.697 (5)	151
C8—H8B⋯O3ⁱ	0.97	2.22	2.996 (6)	136

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

Acknowledgments

Support from the National Natural Science Foundation of China (21163024) is acknowledged.

supplementary crystallographic information

Experimental

The title compound was obtained through the following four steps: 2-fluorobenzoic acid (700 mg, 5 mmol) was dissolved into 3 ml of SOCl₂, the mixture stirred at 1033 K for 5 h and then slowly cooled to room temperature before removing excess SOCl₂. After preparing an ethanol solution (10 ml) of 2-fluorobenzoyl chloride (317 mg, 2 mmol) and 1-boc-piperazine (372 mg, 4 mmol), potassium carbonate (552 mg, 4 mmol) was added to the solution. The mixture was refluxed for 12 h and then cooled to room temperature; extraction and concentration were performed to obtain an oil. After mixing the oil (a dichloromethane solution, 10 ml) with TFA (1.5 ml) and stirring for 12 h to complete the reaction, the mixture was poured into water. The aqueous layer was extracted by ethyl acetate, and then the organic layer was separated, dried using sodium sulfate to obtain 4-(2-fluorobenzoyl)piperazin-1-ium trifluoroacetate. Potassium carbonate (276 mg, 2 mmol) was added to the prepared ethanol solution (10 ml) of (2-fluorophenyl)(piperazin-1-yl)methanone (208 mg, 1 mmol) and 2-chloro-1-(4-hydroxyphenyl)ethanone (341 mg, 2 mmol), which was refluxed for 5 h and mixed by adding water. Again the aqueous layer was extracted by ethyl acetate for the separation of the organic layer, washed using anhydrous ethyl acetate, and dried using sodium sulfate, filtered, and concentrated in vacuum. The purification of residue by using silica gel column chromatography and eluting with EtOAc–petroleum ether (1:1) produced the pale-yellow solid (yield: 164 mg, 48%) of 4-(2-fluorobenzoyl)-1-[2-(4-hydroxyphenyl)-2-oxoethyl]piperazin-1-ium trifluoroacetate.