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Acta Crystallogr Sect E Struct Rep Online. 2009 October 1; 65(Pt 10): o2454.
Published online 2009 September 12. doi:  10.1107/S1600536809036009
PMCID: PMC2970242

3,3′-Dimethyl-1,1′-ethyl­ene­diimidazolium dibromide

Abstract

The title compound, C10H16Br2N4, was synthesized by the reaction of 1-methyl­imidazole and 1,2-dibromo­ethane in toluene. The complete dication is generated by a crystallographic inversion centre situated at the mid-point of the ethane C—C bond. In the crystal structure, weak inter­molecular C—H(...)Br inter­actions link the mol­ecules into chains along the b axis and an intramolecular C—H(...)Br close contact is also present.

Related literature

For general background, see: Ding et al. (2007 [triangle]). For related literature, see: Peveling (2001 [triangle]); Takao & Kazuhiko (1997 [triangle]). For bond-length data, see: Allen et al. (1987 [triangle]).

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Object name is e-65-o2454-scheme1.jpg

Experimental

Crystal data

  • C10H16N4 2+·2Br
  • M r = 352.07
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-o2454-efi1.jpg
  • a = 8.4750 (17) Å
  • b = 8.9620 (18) Å
  • c = 9.2390 (18) Å
  • β = 107.73 (3)°
  • V = 668.4 (3) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 6.05 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 [triangle]) T min = 0.264, T max = 0.583
  • 1296 measured reflections
  • 1212 independent reflections
  • 862 reflections with I > 2σ(I)
  • R int = 0.021
  • 3 standard reflections every 200 reflections intensity decay: 1%

Refinement

  • R[F 2 > 2σ(F 2)] = 0.059
  • wR(F 2) = 0.160
  • S = 1.01
  • 1212 reflections
  • 73 parameters
  • H-atom parameters constrained
  • Δρmax = 0.80 e Å−3
  • Δρmin = −0.85 e Å−3

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1985 [triangle]); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo,1995 [triangle]); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXTL.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809036009/at2872sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809036009/at2872Isup2.hkl

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

Acknowledgments

The authors thank the Center of Testing and Analysis, Nanjing University, for support.

supplementary crystallographic information

Comment

The title compound is a kind of ionic liquids to be used as green alternatives to volatile organic solvents inelectrochemical, synthetic and separation processes. For general background, see: (Ding et al., 2007). We herein report the crystal structure of the title compound (I).

In the molecule of (I), (Fig. 1), the bond lengths (Allen et al., 1987) and angles are within normal ranges. The whole molecule has an inversion symmetry located on the ethane group of the main molecule.

In the crystal structure, weak intermolecular C—H···Br interactions (Table 1) link the molecules into chains along the b axis (Fig.2), in which they may be effective in the stabilization of the structure.

Experimental

The ionic liquid compound was prepared following modified literature procedures (Ding et al., 2007). 1-Methylimidazole (8.21 g, 0.1 mol) was mixed with 1,2-dibromoethane (9.38 g, 0.05 mol) in 100 ml of toluene and refluxed for 24 h; the mixture was cooled to room temperature and filtered. The solids were washed several times with ethyl acetate (800 ml) and the white product dried in vacuum (yield:7.3 g, 54.2%). The product was dissolved in the chloroform and the crystals were obtained by evaporating the chloroform slowly at room temperature for about 9 d.

Refinement

Carbon-bound H atoms were positioned with idealized geometry [aromatic C—H = 0.93 Å, methylene C—H = 0.97 Å and methyl C—H = 0.96 Å] and refined with fixed isotropic displacement parameters [Uiso(H) = 1.5Ueq(H)(methyl C) and Uiso(H) = 1.2Ueq (aromatic and methylene C)] using a riding model.

Figures

Fig. 1.
A drawing of the title molecular structure, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. Atoms labeled with the suffixes A are generated by the symmetry operation ( -x+1, -y+1, -z+1). Hydrogen bonds are ...
Fig. 2.
A packing diagram for (I).

Crystal data

C10H16N42+·2BrF(000) = 348
Mr = 352.07Dx = 1.749 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 25 reflections
a = 8.4750 (17) Åθ = 9–13°
b = 8.9620 (18) ŵ = 6.05 mm1
c = 9.2390 (18) ÅT = 293 K
β = 107.73 (3)°Square, white
V = 668.4 (3) Å30.30 × 0.20 × 0.10 mm
Z = 2

Data collection

Enraf–Nonius CAD-4 diffractometer862 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.021
graphiteθmax = 25.3°, θmin = 2.5°
ω/2θ scansh = 0→10
Absorption correction: ψ scan (North et al., 1968)k = 0→10
Tmin = 0.264, Tmax = 0.583l = −11→10
1296 measured reflections3 standard reflections every 200 reflections
1212 independent reflections intensity decay: 1%

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.059Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.160H-atom parameters constrained
S = 1.01w = 1/[σ2(Fo2) + (0.1P)2 + 0.7P] where P = (Fo2 + 2Fc2)/3
1212 reflections(Δ/σ)max < 0.001
73 parametersΔρmax = 0.80 e Å3
0 restraintsΔρmin = −0.85 e Å3

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

xyzUiso*/Ueq
Br0.71826 (11)0.14503 (9)0.46360 (9)0.0320 (3)
N10.8500 (8)0.6154 (7)0.3322 (7)0.0266 (15)
C10.9914 (11)0.5837 (12)0.2817 (11)0.048 (3)
H1A0.98700.48180.24880.072*
H1B1.09120.59970.36390.072*
H1C0.99040.64860.19870.072*
N20.6231 (8)0.5865 (7)0.3878 (7)0.0224 (14)
C20.7287 (9)0.5215 (9)0.3336 (8)0.0235 (17)
H2A0.72130.42310.30030.028*
C30.6774 (10)0.7310 (9)0.4270 (9)0.0276 (19)
H3A0.62700.80230.47130.033*
C40.8169 (11)0.7482 (9)0.3886 (10)0.035 (2)
H4A0.87960.83490.39870.042*
C50.4817 (10)0.5171 (10)0.4162 (9)0.0265 (18)
H5A0.45440.42550.35810.032*
H5B0.38690.58340.38360.032*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Br0.0506 (5)0.0167 (5)0.0261 (5)0.0002 (4)0.0081 (4)−0.0024 (4)
N10.039 (4)0.018 (4)0.024 (3)−0.007 (3)0.011 (3)−0.008 (3)
C10.044 (5)0.068 (7)0.039 (6)−0.016 (5)0.023 (5)−0.021 (6)
N20.034 (4)0.015 (3)0.015 (3)−0.004 (3)0.003 (3)0.004 (3)
C20.033 (4)0.017 (4)0.018 (4)−0.005 (3)0.004 (3)−0.008 (3)
C30.045 (5)0.011 (4)0.028 (5)−0.003 (3)0.013 (4)0.000 (3)
C40.046 (5)0.018 (4)0.040 (5)−0.012 (4)0.011 (4)−0.009 (4)
C50.029 (4)0.026 (4)0.024 (4)−0.010 (3)0.007 (3)0.001 (4)

Geometric parameters (Å, °)

N1—C21.331 (10)N2—C51.443 (9)
N1—C41.363 (10)C2—H2A0.9300
N1—C11.441 (10)C3—C41.343 (12)
C1—H1A0.9600C3—H3A0.9300
C1—H1B0.9600C4—H4A0.9300
C1—H1C0.9600C5—C5i1.514 (15)
N2—C21.290 (10)C5—H5A0.9700
N2—C31.386 (10)C5—H5B0.9700
C2—N1—C4107.4 (7)N1—C2—H2A124.8
C2—N1—C1126.9 (7)C4—C3—N2106.7 (7)
C4—N1—C1125.8 (7)C4—C3—H3A126.7
N1—C1—H1A109.5N2—C3—H3A126.7
N1—C1—H1B109.5C3—C4—N1107.5 (7)
H1A—C1—H1B109.5C3—C4—H4A126.2
N1—C1—H1C109.5N1—C4—H4A126.2
H1A—C1—H1C109.5N2—C5—C5i110.5 (8)
H1B—C1—H1C109.5N2—C5—H5A109.6
C2—N2—C3108.0 (6)C5i—C5—H5A109.6
C2—N2—C5126.1 (7)N2—C5—H5B109.6
C3—N2—C5125.7 (7)C5i—C5—H5B109.6
N2—C2—N1110.3 (7)H5A—C5—H5B108.1
N2—C2—H2A124.8
C3—N2—C2—N1−0.9 (8)N2—C3—C4—N1−2.0 (9)
C5—N2—C2—N1−175.6 (7)C2—N1—C4—C31.5 (10)
C4—N1—C2—N2−0.4 (9)C1—N1—C4—C3−178.1 (8)
C1—N1—C2—N2179.2 (8)C2—N2—C5—C5i101.3 (10)
C2—N2—C3—C41.8 (9)C3—N2—C5—C5i−72.4 (11)
C5—N2—C3—C4176.5 (7)

Symmetry codes: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C2—H2A···Br0.932.923.591 (8)130
C1—H1B···Brii0.962.973.738 (8)138

Symmetry codes: (ii) −x+2, −y+1, −z+1.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: AT2872).

References

  • Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19.
  • Ding, Y. S., Zha, M., Zhang, J. & Wang, S. S. (2007). Colloids Surf. A: Physicochem. Eng.298, 201–205.
  • Enraf–Nonius (1985). CAD-4 Software Enraf-Nonius, Delft,The Netherlands.
  • Harms, K. & Wocadlo, S. (1995). XCAD4 University of Marburg, Germany.
  • North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359.
  • Peveling, R. (2001). J. Orthopt. Res.10, 171–187.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Takao, S. & Kazuhiko, M. (1997). Takasago International Corporation, Tokyo, Japan. EP Patent No. 0 755 937.

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography