1-{(Z)-1-(2,4-Dichloro­phen­yl)-1-[2-(4-methyl­phen­oxy)eth­oxy]prop-1-en-2-yl}-1H-imidazol-3-ium nitrate

Song Guo; Yong-hong Hu; Yuan-yuan Luan; Lu-lu Wang; Wen-ge Yang

doi:10.1107/S1600536812046181

. 2012 Dec 5;69(Pt 1):o27. doi: 10.1107/S1600536812046181

1-{(Z)-1-(2,4-Dichlorophenyl)-1-[2-(4-methylphenoxy)ethoxy]prop-1-en-2-yl}-1H-imidazol-3-ium nitrate

Song Guo ^a, Yong-hong Hu ^a, Yuan-yuan Luan ^b, Lu-lu Wang ^a, Wen-ge Yang ^a,^*

PMCID: PMC3588376 PMID: 23476414

Abstract

In the title salt, C₂₁H₂₁Cl₂N₂O₂ ⁺·NO₃ ⁻, the imidazole ring makes dihedral angles of 43.39 (14) and 10.9 (2)° with the 4-methylphenyl and 2,4-dichlorophenyl rings, respectively. The molecule adopts a Z conformation about the C=C double bond, which links the imidazole ring to the 4-methylphenoxy unit via an ethoxy chain. In the crystal, cations and anions are linked into chains by N—H⋯O and C—H⋯O hydrogen bonds.

Related literature

For background to azole derivatives and synthetic details, see: Jeu et al. (2003 ▶); Fromtling & Castaner (1996 ▶); Ludwig & Kurt (1985 ▶). For a related structure, see: Kurt et al. (1987 ▶).

Experimental

Crystal data

C₂₁H₂₁Cl₂N₂O₂ ⁺·NO₃ ⁻
M _r = 466.31
Triclinic,
a = 9.5300 (19) Å
b = 9.924 (2) Å
c = 12.449 (3) Å
α = 69.05 (3)°
β = 80.59 (3)°
γ = 88.75 (3)°
V = 1083.9 (4) Å³
Z = 2
Mo Kα radiation
μ = 0.34 mm⁻¹
T = 293 K
0.30 × 0.20 × 0.10 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ▶) T _min = 0.905, T _max = 0.967
4247 measured reflections
3988 independent reflections
2974 reflections with I > 2σ(I)
R _int = 0.020
3 standard reflections every 200 reflections intensity decay: 1%

Refinement

R[F ² > 2σ(F ²)] = 0.048
wR(F ²) = 0.158
S = 1.01
3988 reflections
281 parameters
H-atom parameters constrained
Δρ_max = 0.33 e Å⁻³
Δρ_min = −0.25 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

Click here for additional data file.^{(22.3KB, cif)}

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812046181/pv2548sup1.cif

e-69-00o27-sup1.cif^{(22.3KB, cif)}

Click here for additional data file.^{(195.4KB, hkl)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812046181/pv2548Isup2.hkl

e-69-00o27-Isup2.hkl^{(195.4KB, hkl)}

Click here for additional data file.^{(8.1KB, cml)}

Supplementary material file. DOI: 10.1107/S1600536812046181/pv2548Isup3.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
N2—H2A⋯O4	0.86	2.55	3.218 (5)	135
N2—H2A⋯O5ⁱ	0.86	1.85	2.703 (5)	170
C13—H13A⋯O5ⁱⁱ	0.93	2.37	3.188 (5)	147
C21—H21A⋯O3ⁱⁱ	0.93	2.46	3.337 (5)	157

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

Acknowledgments

This research work was supported by the Program of Six Talent Tops Foundation of Jiangsu Province (2009 NO 2009118) and the Natural Science Basic Research Program of Higher Education in Jiangsu Province (08KJA530002).

supplementary crystallographic information

Comment

Azole derivatives such as Voriconazole and Ketoconazole are safe and effective antifungal agents (Jeu et al., 2003; Fromtling & Castaner,1996). As part of our studies on the synthesis of new azole derivatives, the crystal structure of the title compound was determined.

In the molecular structure of the title compound (Fig. 1) the double bond is Z configurated. 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). The bond lengths and bpnd angles in the title compound agree with the corresponding bond lengths and angles reported for a closely related compound (Kurt et al., 1987).

Experimental

1-(2,4-Dichlorophenyl)-2-(1H-imidazol-1-yl)-1-propanone (16.6 g, 0.06 mol), 30% aqueous sodium hydroxide (50 ml), toluene (100 ml) and tetrabutylammonium hydroxide (0.26g, 0.001mol) were mixed and heated to 343.15 K under vigorous stirring. 1-(2-Bromoethoxy)-4-methyl-benzene (13.3 g, 0.06 mol), dissolved in toluene (70 ml), wais instilled into the stirred and warmed solution in the course of 10 h. The mixture was stirred at room temperature, and monitored by TLC until the reaction was complete. 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 is diluted with 100 ml ethanol and then adjusted to a pH-value of 2 by means of 65% aqueous nitric acid. The derived nitric acid solution was cooled in the refrigerator. The impure precipitated product herein was subsequently crystallized from isopropanol. The purified product was analytically identified as an approximately pure Z-isomer of propylene nitrate. Crystals of 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).