1-[(Z)-8-(4-Chlorophenoxy)-3-(2,4-di­fluorophenyl)-4-oxaocta-2-en-2-yl]-1H-1,2,4-triazol-4-ium nitrate

Jian-long Chen; Kai Wang; Yan Shen; Li-li Ren; Guo-guang Chen

doi:10.1107/S1600536811038761

. 2011 Sep 30;67(Pt 10):o2800. doi: 10.1107/S1600536811038761

1-[(Z)-8-(4-Chlorophenoxy)-3-(2,4-difluorophenyl)-4-oxaocta-2-en-2-yl]-1H-1,2,4-triazol-4-ium nitrate

Jian-long Chen ^a,^*, Kai Wang ^b, Yan Shen ^a, Li-li Ren ^a, Guo-guang Chen ^a

PMCID: PMC3201435 PMID: 22065050

Abstract

In the title compound C₂₁H₂₁ClF₂N₃O₂ ⁺·NO₃ ⁻, the triazole ring makes dihedral angles of 40.7 (3) and 30.2 (4)° with the 4-chloropheny and 2,4-difluorophenyl rings, respectively. The cation adopts a Z-configuration about the C=C double bond which links the triazole ring to the 4-chlorophenoxy unit via a butyloxy chain. In the crystal, the cations and the anions are linked by N—H⋯O, C—H⋯O and C—H⋯F hydrogen bonding.

Related literature

For the antifungal activity of related compounds, see: Jeu et al. (2003 ▶). For details of the synthesis, see: Ludwig & Kurt (1985 ▶). For a related structure, see: Kurt et al. (1987 ▶).

Experimental

Crystal data

C₂₁H₂₁ClF₂N₃O₂ ⁺·NO₃ ⁻
M _r = 482.87
Monoclinic,
a = 7.9580 (16) Å
b = 31.635 (6) Å
c = 9.1850 (18) Å
β = 97.29 (3)°
V = 2293.6 (8) Å³
Z = 4
Mo Kα radiation
μ = 0.22 mm⁻¹
T = 293 K
0.30 × 0.10 × 0.10 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ▶) T _min = 0.936, T _max = 0.978
4521 measured reflections
4216 independent reflections
1952 reflections with I > 2σ(I)
R _int = 0.092
3 standard reflections every 200 reflections intensity decay: 1%

Refinement

R[F ² > 2σ(F ²)] = 0.066
wR(F ²) = 0.140
S = 1.00
4216 reflections
298 parameters
H-atom parameters constrained
Δρ_max = 0.20 e Å⁻³
Δρ_min = −0.24 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/S1600536811038761/pv2445sup1.cif

e-67-o2800-sup1.cif^{(22.5KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811038761/pv2445Isup2.hkl

e-67-o2800-Isup2.hkl^{(206.6KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811038761/pv2445Isup3.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⋯O5	0.86	1.80	2.659 (4)	174
C9—H9A⋯F1ⁱ	0.96	2.53	3.371 (5)	146
C10—H10A⋯O4ⁱⁱ	0.93	2.28	3.033 (5)	137
C1—H1A⋯O3ⁱⁱⁱ	0.93	2.57	3.434 (5)	155
C11—H11A⋯O5ⁱⁱⁱ	0.93	2.25	3.180 (5)	174

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

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) As part of our studies on the synthesis of new triazole derivatives, the crystal structure of the title compound, having similar structure with omoconazol (Kurt et al., 1987), was determined.

In the title compound (Fig. 1), the cation adopts a Z conformation about the C═C double bond. In the crystal structure the anions and cations are connected via N—H···O, C—H···O and C—H···F hydrogen bonding (Table 1 and Fig. 2).

Experimental

1-(2,4-Difluorophenyl)-2-(1,2,4-triazol)-1-y1)propan-1-one (3.0 g, 0.01 mol) 10 g of a 50% aqueous sodium hydroxide, toluene (15 ml) and 1.5 ml of a 40% aqueous solution of tetrabutyl ammonium hydroxide were mixed and heated to 323 K under vigorous stirring. 1-Bromo-4-(4-chlorophenoxy)-butane (2.6 g, 0.01 mol) dissolved in 10 ml toluene, was instilled into the stirred and warmed solution in the course of 10 h. The mixture was subsequently stirred for another 20 h at 323 K. The reaction mixture was mixed with as much water and chloroform so that the aqueous phase becomes lighter than the organic phase. Thereafter, the organic and aqueous phases were separated. The organic phase was dried with sodium sulfate. The solvents were distilled under reduced pressure. The remaining residue was a dark oil that was diluted with 10 ml 2-propanol and then adjusted to a pH-value of 2 by 30% aqueous nitric acid. The resulting nitric acid solution was then cooled in the refrigerator. The impure precipitated product herein was subsequently crystallized from a 1:1 mixture of ethyl acetate and ethanol. The purified product was analytically identified as an approximately pure Z-isomer of the title compound. Crystals of the title compound suitable for X-ray diffraction were obtained by slow evaporation of an ethanol solution. Details on the synthesis can be found in the literature (Ludwig & Kurt, 1985).