1-{(Z)-1-[3-(4-Bromo­phen­oxy)prop­oxy]-1-(2,4-difluoro­phen­yl)prop-1-en-2-yl}-1H-1,2,4-triazol-4-ium nitrate

Fei Shen; Song Guo; Yuan-yuan Luan; Kai Wang; Yong-hong Hu

doi:10.1107/S1600536812024154

. 2012 Jun 13;68(Pt 7):o2010. doi: 10.1107/S1600536812024154

1-{(Z)-1-[3-(4-Bromophenoxy)propoxy]-1-(2,4-difluorophenyl)prop-1-en-2-yl}-1H-1,2,4-triazol-4-ium nitrate

Fei Shen ^a, Song Guo ^a, Yuan-yuan Luan ^b, Kai Wang ^a, Yong-hong Hu ^a,^*

PMCID: PMC3393281 PMID: 22807838

Abstract

In the title molecular salt, C₂₀H₁₉BrF₂N₃O₂ ⁺·NO₃ ⁻, the N atom at position 4 of the heterocyclic ring is protonated. The triazole ring makes dihedral angles of 96.6 (4) and 54.4 (3)° with the 4-bromophenyl and 2,4-difluorophenyl rings, respectively, and the molecule adopts a Z conformation about the C=C double bond. In the crystal, cations and anions are linked by N—H⋯O and C—H⋯O hydrogen bonds.

Related literature

For background to the uses of triazole derivatives, see: Jeu et al. (2003 ▶); Fromtling & Castaner (1996 ▶). For further synthetic details, see: Ludwig & Kurt (1985 ▶).

Experimental

Crystal data

C₂₀H₁₉BrF₂N₃O₂ ⁺·NO₃ ⁻
M _r = 513.30
Triclinic,
a = 8.3030 (17) Å
b = 8.4260 (17) Å
c = 16.170 (3) Å
α = 91.10 (3)°
β = 95.80 (3)°
γ = 102.30 (3)°
V = 1098.7 (4) Å³
Z = 2
Mo Kα radiation
μ = 1.93 mm⁻¹
T = 293 K
0.20 × 0.10 × 0.10 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ▶) T _min = 0.699, T _max = 0.831
4329 measured reflections
4029 independent reflections
2250 reflections with I > 2σ(I)
R _int = 0.032
3 standard reflections every 200 reflections intensity decay: 1%

Refinement

R[F ² > 2σ(F ²)] = 0.063
wR(F ²) = 0.152
S = 1.01
4029 reflections
289 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.49 e Å⁻³
Δρ_min = −0.47 e Å⁻³

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994 ▶); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995 ▶); 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: PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812024154/hb6699sup1.cif

e-68-o2010-sup1.cif^{(22.1KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812024154/hb6699Isup2.hkl

e-68-o2010-Isup2.hkl^{(197.4KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812024154/hb6699Isup3.cml

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
N3—H3A⋯O4	0.86	1.95	2.790 (6)	167
C9—H9A⋯O3ⁱ	0.93	2.55	3.271 (7)	135
C10—H10A⋯O3ⁱⁱ	0.93	2.49	3.263 (7)	140
C10—H10A⋯O5ⁱⁱ	0.93	2.42	3.340 (7)	168
C19—H19A⋯O3	0.93	2.54	3.276 (7)	137

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

Acknowledgments

This research work was supported by the Specialized Research Fund for the Doctoral Program of Higher Education (grant No. 20113221110005).

supplementary crystallographic information

Comment

Triazole derivatives such as Voriconazole ((2R,3S)-2-(2,4-difluorophenyl) -3-(5-fluoropyrimidin-4-yl)-1-(1H-1,2,4-triazol-1-yl) butan-2-ol) and Posaconazole (4-(4-(4-(4-(((3R,5R)-5-(2,4-difluorophenyl)-5-(1,2,4- triazol-1-ylmethyl)oxolan-3-yl)methoxy)phenyl)piperazin-1-yl)phenyl)- 2-((2S,3S)-2-hydroxypentan-3-yl)-1,2,4-triazol-3-one) are safe and effective antifungal agents. (Jeu et al., 2003; Fromtling & Castaner, 1996) As part of our studies on the synthesis of new triazole derivatives, the crystal structure of the title compound was determined.

In the molecular structure of the title compound the double bond has a Z conformation. In the crystal structure the anions and cations are connected via N—H···O and C—H···O hydrogen bonding (Table 1 and Fig. 2).

Experimental

3 g (0.01 mol) 1-(2,4-difluorophenyl)-2-(1,2,4-triazol)-1-y1)propan-1-one, 10 g of a 50% aqueous sodium hydroxide, 15 ml toluene and 1.5 ml of a 40% aqueous solution of tetrabutyl ammonium hydroxide are mixed and heated to 323.15 K under vigorous stirring. 2.93 g (0.01 mol) 1-bromo-3-(4-bromophenoxy)-propane, dissolved in 10 ml toluene, is instilled into the stirred and warmed solution in the course of 10 h. The mixture is subsequently stirred for another 20 h at 323.15 K. The reaction mixture is mixed with as much water and chloroform so that the aqueous phase becomes lighter than the organic phase. Thereafter, the organic and aqueous phases are separated. The organic phase is dried with sodium sulfate. The solvents are distilled under reduced pressure. The remaining residue is a dark oil that is diluted with 10 ml 2-propanol and then adjusted to a PH-value of 2 by means of 30% aqueous nitric acid. The thus derived nitric acid solution is then cooled in the refrigerator. The impure precipitated product herein is subsequently crystallized from a 1:1 mixture of ethyl acetate and ethanol. The purified product may be analytically identified as an approximately pure Z-isomer of propylene nitrate. Colourless plates of the title compound were obtained by slow evaporation of an ethanol solution. Details on the synthesis can be found in the literature reported by Ludwig & Kurt (1985).