1-Benzyl-3-methyl­imidazolium chloride 0.25-hydrate

Xiujie Ji; Bowen Cheng; Jun Song; Chao Liu

doi:10.1107/S1600536809053306

. 2009 Dec 19;66(Pt 1):o218. doi: 10.1107/S1600536809053306

1-Benzyl-3-methylimidazolium chloride 0.25-hydrate

Xiujie Ji ^a, Bowen Cheng ^a,^*, Jun Song ^a, Chao Liu ^b

PMCID: PMC2980248 PMID: 21580102

Abstract

The asymmetric unit of the title compound, C₁₁H₁₃N₂ ⁺·Cl⁻, contains two independent ion pairs and and half a solvent water molecule (m site symmetry for the O atom). The imidazole ring is oriented at dihedral angles of 66.61 (3) and 89.17 (3)° with respect to the aromatic ring in the two cations. In the crystal, O—H⋯(O,Cl) hydrogen bonds and π–π stacking interactions between the imidazole ring of one molecule and the aromatic ring of another [perpendicular distance = 3.4 (4) Å] link the molecules.

Related literature

For general background to ionic liquids, see: Fukaya et al. (2006 ▶); Ranu et al. (2005 ▶); Chen et al. (2005 ▶); Blanchard et al. (2001 ▶); Zhang et al. (2006 ▶); Katayanagi et al. (2004 ▶). For bond-length data, see: Allen et al. (1987 ▶).

Experimental

Crystal data

C₁₁H₁₃N₂ ⁺·Cl⁻·0.25H₂O
M _r = 213.19
Orthorhombic,
a = 11.452 (2) Å
b = 11.410 (2) Å
c = 34.867 (7) Å
V = 4555.8 (16) Å³
Z = 16
Mo Kα radiation
μ = 0.30 mm⁻¹
T = 113 K
0.22 × 0.20 × 0.16 mm

Data collection

Rigaku Saturn diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2000 ▶) T _min = 0.937, T _max = 0.953
30046 measured reflections
4022 independent reflections
3619 reflections with I > 2σ(I)
R _int = 0.041

Refinement

R[F ² > 2σ(F ²)] = 0.042
wR(F ²) = 0.119
S = 1.08
4022 reflections
268 parameters
3 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.30 e Å⁻³
Δρ_min = −0.28 e Å⁻³

Data collection: CrystalClear (Rigaku, 2000 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶) and PLATON (Spek, 2009 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809053306/bq2176sup1.cif

e-66-0o218-sup1.cif^{(21.9KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809053306/bq2176Isup2.hkl

e-66-0o218-Isup2.hkl^{(197.2KB, 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
O1—H1E⋯O1ⁱ	0.86 (1)	1.81 (4)	2.434 (7)	128 (4)
O1—H1E⋯Cl2ⁱ	0.86 (1)	2.51 (3)	3.179 (3)	135 (4)

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Symmetry code: (i) Inline graphic .

Acknowledgments

We thank the China Postdoctoral Science Foundation (No. 20080440684), the Tianjin Municipal Natural Science Foundation (No. 09JCZDJC22700) and the Hebei Province Natural Science Foundation (No. E2009000081) for financial support.

supplementary crystallographic information

Comment

Ionic liquids (ILs) are a class of compounds composed of organic cations and organic or inorganic anions and have attracted significant attention due to their beneficial properties and their low impact on environment. Many investigations have been dedicated to their use as new media for synthetic chemistry (Fukaya et al., 2006), catalysts for organic synthesis (Ranu et al., 2005; Chen et al., 2005), extractants for separation science (Blanchard et al., 2001) and electrolytes for electrochemistry (Zhang et al., 2006) as well as other areas due to their peculiar physical properties such as a wide liquid range, non-volatility, chemical stability and large windows of electrochemistry. Because it is technically difficult for ionic liquid to grow single crystal and to select suitable sample for single crystal x-ray diffraction at low temperature, so far a few crystal structures have been determined by x-ray diffraction (Katayanagi et al., 2004). We have synthesized a numer of ionic liquids. The title compound is one of the products, and we report herein its crystal structure.

In the molecule of the title compound (Fig. 1) the bond lengths (Allen et al., 1987) and angles are within normal ranges. The imidazole ring is oriented with respect to the aromatic ring at a dihedral angle of 89.17 (3)° and 66.61 (3)°, respectively. The hydrogen bond are formed between one Cl and H₂O (Table 1). In the crystal structure, π-π packing between the imidazole ring of one molecule and the aromatic ring of the other [perpendicular distance = 3.4 (4)Å] link the molecules. The packing diagram of the O-H···Cl bonds is shown in Fig. 2.

Experimental

For the preparation of the title compound, N-methylimidazole (8.2 g, 0.1 mol) was dissolved in dry acetonitrile (30 ml). Benzyl chloride (12.7 g, 0.1 mol) was added to this solution, the reaction was stirred under reflux for 7 h. The reaction mixture was extracted with ethyl acetate. After concentration, the residue was purified by recrystallization from chloroform (yield; 19.4 g, 93%, m.p. 251 K). Spectroscopic analysis: IR (KBr, ν, cm^-1): 3415, 3085, 2927, 1634, 1571, 1455, 1160, 824, 722. Analysis required for C₂₂H₂₇Cl₂N₄O_0.5: C 61.97; H 6.38; N 13.14%. Found: C 61.92; H 6.40; N 13.10%.