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

Chen, Y.; Song, W.; Xu, J.; Cui, R.; Tian, D.

doi:10.1107/S1600536809036009

organic compounds

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ISSN: 2056-9890

Volume 65| Part 10| October 2009| Page o2454

doi:10.1107/S1600536809036009

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

Yu Chen,^a Wei Song,^a Juan Xu,^a Rui-bo Cui ^a and Dan-bi Tian ^a ^*

^aDepartment of Applied Chemistry, College of Science, Nanjing University of Technology, Nanjing 210009, People's Republic of China
^*Correspondence e-mail: danbi@njut.edu.cn

(Received 28 August 2009; accepted 6 September 2009; online 12 September 2009)

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 ). For related literature, see: Peveling (2001 ); Takao & Kazuhiko (1997 ). For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₁₀H₁₆N₄²⁺·2Br⁻
M_r = 352.07
Monoclinic, P 2₁ /c
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 ) 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[F² > 2σ(F²)] = 0.059
wR(F²) = 0.160
S = 1.01
1212 reflections
73 parameters
H-atom parameters constrained
Δρ_max = 0.80 e Å⁻³
Δρ_min = −0.85 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2A⋯Br	0.93	2.92	3.591 (8)	130
C1—H1B⋯Brⁱ	0.96	2.97	3.738 (8)	138
Symmetry code: (i) -x+2, -y+1, -z+1.

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1985 ); 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: SHELXTL.

Supporting information

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

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

checkCIF report

Comment top

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.

Related literature top

The title compound is a kind of ionic liquid which can be used as a green alternative to volatile organic solvents in electrochemical, synthetic and separation processes. For general background, see: Ding et al. (2007). For related literature [on what subject?], see: Peveling (2001); Takao & Kazuhiko (1997). For bond-length data, see: Allen et al. (1987).

Experimental top

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.

Computing details top

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1985); cell refinement: CAD-4 EXPRESS (Enraf–Nonius, 1985); 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: SHELXTL (Sheldrick, 2008).

Figures top

	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 shown by dashed lines.
	Fig. 2. A packing diagram for (I).

3,3'-Dimethyl-1,1'-ethylenediimidazolium dibromide top

Crystal data top

C₁₀H₁₆N₄²⁺·2Br⁻	F(000) = 348
M_r = 352.07	D_x = 1.749 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 25 reflections
a = 8.4750 (17) Å	θ = 9–13°
b = 8.9620 (18) Å	µ = 6.05 mm⁻¹
c = 9.2390 (18) Å	T = 293 K
β = 107.73 (3)°	Square, white
V = 668.4 (3) Å³	0.30 × 0.20 × 0.10 mm
Z = 2

Data collection top

Enraf–Nonius CAD-4 diffractometer	862 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.021
Graphite monochromator	θ_max = 25.3°, θ_min = 2.5°
ω/2θ scans	h = 0→10
Absorption correction: ψ scan (North et al., 1968)	k = 0→10
T_min = 0.264, T_max = 0.583	l = −11→10
1296 measured reflections	3 standard reflections every 200 reflections
1212 independent reflections	intensity decay: 1%

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.059	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.160	H-atom parameters constrained
S = 1.01	w = 1/[σ²(F_o²) + (0.1P)² + 0.7P] where P = (F_o² + 2F_c²)/3
1212 reflections	(Δ/σ)_max < 0.001
73 parameters	Δρ_max = 0.80 e Å⁻³
0 restraints	Δρ_min = −0.85 e Å⁻³

Crystal data top

C₁₀H₁₆N₄²⁺·2Br⁻	V = 668.4 (3) Å³
M_r = 352.07	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 8.4750 (17) Å	µ = 6.05 mm⁻¹
b = 8.9620 (18) Å	T = 293 K
c = 9.2390 (18) Å	0.30 × 0.20 × 0.10 mm
β = 107.73 (3)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	862 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.021
T_min = 0.264, T_max = 0.583	3 standard reflections every 200 reflections
1296 measured reflections	intensity decay: 1%
1212 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.059	0 restraints
wR(F²) = 0.160	H-atom parameters constrained
S = 1.01	Δρ_max = 0.80 e Å⁻³
1212 reflections	Δρ_min = −0.85 e Å⁻³
73 parameters

Special details top

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) top

	x	y	z	U_iso*/U_eq
Br	0.71826 (11)	0.14503 (9)	0.46360 (9)	0.0320 (3)
N1	0.8500 (8)	0.6154 (7)	0.3322 (7)	0.0266 (15)
C1	0.9914 (11)	0.5837 (12)	0.2817 (11)	0.048 (3)
H1A	0.9870	0.4818	0.2488	0.072*
H1B	1.0912	0.5997	0.3639	0.072*
H1C	0.9904	0.6486	0.1987	0.072*
N2	0.6231 (8)	0.5865 (7)	0.3878 (7)	0.0224 (14)
C2	0.7287 (9)	0.5215 (9)	0.3336 (8)	0.0235 (17)
H2A	0.7213	0.4231	0.3003	0.028*
C3	0.6774 (10)	0.7310 (9)	0.4270 (9)	0.0276 (19)
H3A	0.6270	0.8023	0.4713	0.033*
C4	0.8169 (11)	0.7482 (9)	0.3886 (10)	0.035 (2)
H4A	0.8796	0.8349	0.3987	0.042*
C5	0.4817 (10)	0.5171 (10)	0.4162 (9)	0.0265 (18)
H5A	0.4544	0.4255	0.3581	0.032*
H5B	0.3869	0.5834	0.3836	0.032*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br	0.0506 (5)	0.0167 (5)	0.0261 (5)	0.0002 (4)	0.0081 (4)	−0.0024 (4)
N1	0.039 (4)	0.018 (4)	0.024 (3)	−0.007 (3)	0.011 (3)	−0.008 (3)
C1	0.044 (5)	0.068 (7)	0.039 (6)	−0.016 (5)	0.023 (5)	−0.021 (6)
N2	0.034 (4)	0.015 (3)	0.015 (3)	−0.004 (3)	0.003 (3)	0.004 (3)
C2	0.033 (4)	0.017 (4)	0.018 (4)	−0.005 (3)	0.004 (3)	−0.008 (3)
C3	0.045 (5)	0.011 (4)	0.028 (5)	−0.003 (3)	0.013 (4)	0.000 (3)
C4	0.046 (5)	0.018 (4)	0.040 (5)	−0.012 (4)	0.011 (4)	−0.009 (4)
C5	0.029 (4)	0.026 (4)	0.024 (4)	−0.010 (3)	0.007 (3)	0.001 (4)

Geometric parameters (Å, º) top

N1—C2	1.331 (10)	N2—C5	1.443 (9)
N1—C4	1.363 (10)	C2—H2A	0.9300
N1—C1	1.441 (10)	C3—C4	1.343 (12)
C1—H1A	0.9600	C3—H3A	0.9300
C1—H1B	0.9600	C4—H4A	0.9300
C1—H1C	0.9600	C5—C5ⁱ	1.514 (15)
N2—C2	1.290 (10)	C5—H5A	0.9700
N2—C3	1.386 (10)	C5—H5B	0.9700

C2—N1—C4	107.4 (7)	N1—C2—H2A	124.8
C2—N1—C1	126.9 (7)	C4—C3—N2	106.7 (7)
C4—N1—C1	125.8 (7)	C4—C3—H3A	126.7
N1—C1—H1A	109.5	N2—C3—H3A	126.7
N1—C1—H1B	109.5	C3—C4—N1	107.5 (7)
H1A—C1—H1B	109.5	C3—C4—H4A	126.2
N1—C1—H1C	109.5	N1—C4—H4A	126.2
H1A—C1—H1C	109.5	N2—C5—C5ⁱ	110.5 (8)
H1B—C1—H1C	109.5	N2—C5—H5A	109.6
C2—N2—C3	108.0 (6)	C5ⁱ—C5—H5A	109.6
C2—N2—C5	126.1 (7)	N2—C5—H5B	109.6
C3—N2—C5	125.7 (7)	C5ⁱ—C5—H5B	109.6
N2—C2—N1	110.3 (7)	H5A—C5—H5B	108.1
N2—C2—H2A	124.8

C3—N2—C2—N1	−0.9 (8)	N2—C3—C4—N1	−2.0 (9)
C5—N2—C2—N1	−175.6 (7)	C2—N1—C4—C3	1.5 (10)
C4—N1—C2—N2	−0.4 (9)	C1—N1—C4—C3	−178.1 (8)
C1—N1—C2—N2	179.2 (8)	C2—N2—C5—C5ⁱ	101.3 (10)
C2—N2—C3—C4	1.8 (9)	C3—N2—C5—C5ⁱ	−72.4 (11)
C5—N2—C3—C4	176.5 (7)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2A···Br	0.93	2.92	3.591 (8)	130
C1—H1B···Brⁱⁱ	0.96	2.97	3.738 (8)	138

Symmetry code: (ii) −x+2, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	C₁₀H₁₆N₄²⁺·2Br⁻
M_r	352.07
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	8.4750 (17), 8.9620 (18), 9.2390 (18)
β (°)	107.73 (3)
V (Å³)	668.4 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	6.05
Crystal size (mm)	0.30 × 0.20 × 0.10

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.264, 0.583
No. of measured, independent and observed [I > 2σ(I)] reflections	1296, 1212, 862
R_int	0.021
(sin θ/λ)_max (Å⁻¹)	0.601

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.059, 0.160, 1.01
No. of reflections	1212
No. of parameters	73
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.80, −0.85

Computer programs: CAD-4 EXPRESS (Enraf–Nonius, 1985), XCAD4 (Harms & Wocadlo,1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2A···Br	0.9300	2.9200	3.591 (8)	130.00
C1—H1B···Brⁱ	0.9600	2.9690	3.738 (8)	138.07

Symmetry code: (i) −x+2, −y+1, −z+1.

Acknowledgements

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

References

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