1,3-Bis(4-methoxy­phen­yl)imidazolidium chloride monohydrate

Yu Wan; Haiqiang Xin; Xiumei Chen; Huahong Xu; Hui Wu

doi:10.1107/S1600536808033965

. 2008 Oct 22;64(Pt 11):o2159. doi: 10.1107/S1600536808033965

1,3-Bis(4-methoxyphenyl)imidazolidium chloride monohydrate

Yu Wan ^a, Haiqiang Xin ^a, Xiumei Chen ^a, Huahong Xu ^a, Hui Wu ^a,^*

PMCID: PMC2959710 PMID: 21581019

Abstract

The asymmetric unit of the title compound, C₁₇H₁₇N₂O₂ ⁺·Cl⁻·H₂O, contains one-half of the cation, one-half of a water molecule and a chloride anion. The complete cation is generated by crystallographic two-fold symmetry, with one C atom lying on the rotation axis. The O and Cl atoms have site symmetry 2. The imidazolidium ring is oriented at a dihedral angle of 4.15 (3)° with respect to the 4-methoxyphenyl ring and an intramolecular C—H⋯O interaction occurs. In the crystal structure, intermolecular O—H⋯Cl and C—H⋯Cl hydrogen bonds link the molecules. There is a π–π contact between the imidazolidium and 4-methoxyphenyl rings [centroid-to-centroid distance = 3.625(3 Å]. There is also a C—H⋯π contact between the methyl group and the 4-methoxyphenyl ring.

Related literature

For general background, see: Lin & Vasam (2005 ▶). For bond-length data, see: Allen et al. (1987 ▶).

Experimental

Crystal data

C₁₇H₁₇N₂O₂ ⁺·Cl⁻·H₂O
M _r = 334.79
Monoclinic,
a = 15.6706 (19) Å
b = 9.4198 (9) Å
c = 5.4026 (4) Å
β = 90.156 (1)°
V = 797.50 (14) Å³
Z = 2
Mo Kα radiation
μ = 0.26 mm⁻¹
T = 298 (2) K
0.20 × 0.11 × 0.09 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.951, T _max = 0.977
2026 measured reflections
749 independent reflections
688 reflections with I > 2σ(I)
R _int = 0.021

Refinement

R[F ² > 2σ(F ²)] = 0.029
wR(F ²) = 0.076
S = 1.01
749 reflections
107 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.11 e Å⁻³
Δρ_min = −0.22 e Å⁻³

Data collection: SMART (Bruker, 1998 ▶); cell refinement: SAINT (Bruker, 1999 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶) and PLATON (Spek, 2003 ▶); software used to prepare material for publication: SHELXTL (Sheldrick, 2008 ▶) and PLATON.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808033965/hk2542sup1.cif

e-64-o2159-sup1.cif^{(15.6KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808033965/hk2542Isup2.hkl

e-64-o2159-Isup2.hkl^{(37.3KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

Cg2 is the centroid of the C3–C8 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2⋯Cl1	0.85	2.29	3.133 (3)	173
C1—H1⋯O2	0.93	2.13	3.060 (3)	180
C2—H2A⋯Cl1ⁱ	0.93	2.69	3.474 (3)	142
C4—H4⋯O2	0.93	2.47	3.391 (3)	170
C9—H9C⋯Cg2ⁱⁱ	0.96	2.91	3.629 (3)	133

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

Acknowledgments

The authors are grateful to the National Natural Science Foundation of China (grant No. 20772103), the Natural Science Foundation of Jiangsu Province (grant No. BK 2007028) and the Surpassing Project of Jiangsu Province (grant No. CX07S_016z) for financial support.

supplementary crystallographic information

Comment

Imidazole and its derivatives such as imidazolium cation are important compounds playing important roles in medical, organic and material chemistry (Lin & Vasam, 2005). A broad application of imidazolium now is to synthesize ionic liquids. Recently, ionic liquids are attracting much attention as alternative reaction media for synthesis and catalysis. Its applications in many different areas including separation processes, catalyst, electrochemistry, electrolytes in solar cells and lubricants are widely recognized. Therefore, the need of ionic liquids with specific chemical and physical properties become stronger. We report herein the synthesis and crystal structure of the title compound.

The asymmetric unit of the title compound (Fig. 1) contains one half-molecule, one half-water molecule and a chloride atom. The bond lengths (Allen et al., 1987) and angles are within normal ranges. Rings A (N1/N1'/C1/C2/C2') and B (C3–C8) are, of course, planar and the dihedral angle between them is A/B = 4.15 (3)° [symmetry code: (') -x, y, -z]. Intramolecular C—H···O and O—H···Cl hydrogen bonds (Table 1) link the molecules.

In the crystal structure, intramolecular C—H···O and O—H···Cl and intermolecular C—H···Cl hydrogen bonds (Table 1) link the molecules (Fig. 2), in which they may be effective in the stabilization of the structure. The π–π contact between the imidazolidium and 4-methoxyphenyl rings, Cg1···Cg2ⁱ [symmetry code: (i) 1 - x, y, 1 - z, where Cg1 and Cg2 are the centroids of the rings A (N1/N1'/C1/C2/C2') and B (C3–C8), respectively] may further stabilize the structure, with centroid-centroid distance of 3.625 (3) Å. There also exist a C—H···π contact (Table 1) between the methyl group and the 4-methoxyphenyl ring.

Experimental

The reaction of 4-methoxybenzenamine (2 mmol) with formaldehyde (aq. 37%, 1 mmol) and glyoxal (aq. 40%, 1 mmol) in ethanol (95%) at 273–278 K for 8 h afforded 1-(2,3-diethoxy-4-(4-methoxyphenyl)cyclopentyl)-4-methoxybenzene (yield; 89%). The title compound was obtained through the oxidization of 1-(2,3-diethoxy-4-(4-methoxyphenyl)cyclopentyl)-4-methoxybenzene by phosgene in DMF at 268–273 K (yield 95%).