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ISSN: 2056-9890

3,3′-Di­methyl-1,1′-methyl­ene­diimidazolium dibromide

aKey Laboratory of Colloid and Interface Chemistry, Shandong University, Jinan 250100, People's Republic of China, and bCollege of Chemistry and Chemical Engineering, Liaocheng University, Liaocheng 252059, People's Republic of China
*Correspondence e-mail: lqzheng@sdu.edu.cn

(Received 4 July 2009; accepted 22 July 2009; online 29 July 2009)

In the crystal structure of the title compound, C9H14N42+·2Br, the cation and anions have crystallographic mirror symmetry, with the mirror plane running through the central CH2 group for the cation. The latter are stacked along the a axis, forming channels hosting the bromide anions. The crystal packing is stabilized by C—H⋯Br hydrogen-bonding inter­actions, generating a two-dimensional network.

Related literature

For related structures, see: Jin et al. (2007[Jin, H.-S., Wang, H.-J., Zhang, Y., Zuo, Y.-J. & Zhong, C.-M. (2007). Acta Cryst. E63, o1880-o1881.]); Eicher et al. (2003[Eicher, T., Hauptmann, S. & Speicher, A. (2003). The Chemistry of Heterocycles: Structures, Reactions, Synthesis and Applications, 2th ed. Weinheim: Wiley-VCH.]).

[Scheme 1]

Experimental

Crystal data
  • C9H14N42+·2Br

  • Mr = 338.06

  • Monoclinic, P 21 /m

  • a = 4.7310 (5) Å

  • b = 11.3861 (12) Å

  • c = 11.8419 (15) Å

  • β = 93.672 (1)°

  • V = 636.59 (12) Å3

  • Z = 2

  • Mo Kα radiation

  • μ = 6.34 mm−1

  • T = 298 K

  • 0.32 × 0.10 × 0.07 mm

Data collection
  • Bruker SMART diffractometer

  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996[Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.]) Tmin = 0.227, Tmax = 0.638

  • 3349 measured reflections

  • 1188 independent reflections

  • 928 reflections with I > 2σ(I)

  • Rint = 0.031

Refinement
  • R[F2 > 2σ(F2)] = 0.028

  • wR(F2) = 0.066

  • S = 1.07

  • 1188 reflections

  • 74 parameters

  • H-atom parameters constrained

  • Δρmax = 0.63 e Å−3

  • Δρmin = −0.27 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
C4—H4⋯Br1i 0.93 2.84 3.724 (3) 158
C3—H3⋯Br1ii 0.93 2.81 3.699 (3) 160
C1—H1A⋯Br1iii 0.97 2.76 3.723 (4) 172
C2—H2⋯Br2iv 0.93 2.82 3.627 (3) 146
C1—H1B⋯Br2iv 0.97 2.81 3.652 (5) 146
Symmetry codes: (i) -x+1, -y+1, -z; (ii) x+1, y, z; (iii) -x, -y+1, -z; (iv) x-1, y, z.

Data collection: SMART (Siemens, 1996[Siemens (1996). SMART and SAINT. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Siemens, 1996[Siemens (1996). SMART and SAINT. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); software used to prepare material for publication: SHELXTL.

Supporting information


Comment top

The title compound was synthesized as the precursor of a chelating N-heterocyclic carbene ligand, which can be generated by deprotonating the ring between the two N atoms of the two imidazolium cations.(Jin et al., 2007).

The structure consists of dimethylethylenediimidazolium cations and bromide anions (Fig. 1). The cation has crystallographically imposed mirror symmetry, with atom C1 located on a mirror plane. Both independent bromide anions also lie on a mirror plane. The C1—N1 bond length is 1.455 (4) Å, and the N1—C1—N1 bond angle is 111.0 (4)°. The C2—N1—C4 bond angle of 108.4 (3)° is similar to those observed in free imidazole (Eicher et al., 2003). The relative orientation of the imidazolium ring with respect to the other imidazolium ring can be described by the value of -95.4 (4)° of the C2—N1—C1—N1 torsion angle. In the crystal, the cations are stacked along the a axis forming channels that are occupied by the bromide anions (Fig. 2). Adjacent molecules are connected into a two-dimensional network through C—H···Br hydrogen interactions (Table 1).

Related literature top

For related structures, see: Jin et al. (2007); Eicher et al. (2003).

Experimental top

A mixture of 1-methylimidazole (0.1 mol) and dichloromethane (0.05 mol) was reacted under nitrogen atmosphere with stirring at 350 K for 48 h. The resulting clear solution was evaporated under vacuum. Colourless crystals suitable for X-ray analysis were obtained by slow evaporation of a ethyl acetate solution over a period of two weeks. (yield 83%) Anal. Calcd (%) for C9H14Br2N4 (Mr = 338.06): C, 32.03; H, 4.09; N, 16.62. Found (%): C, 31.95; H, 4.14; N, 16.57.

Refinement top

All H atoms were placed geometrically and treated as riding on their parent atoms, with C—H = 0.93–0.97 Å, and with Uiso(H) = 1.2Ueq(C) or 1.5Ueq(C) for methyl H atoms.

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT (Siemens, 1996); 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
[Figure 1] Fig. 1. The molecular structure of the compound, with atom labels and 50% probability displacement ellipsoids. Unlabelled atoms are related to labelled atoms by (x, 0.5-y, z)
[Figure 2] Fig. 2. Crystal packing of the compound, showing the two-dimensional network structure formed by C—H···Br hydrogen bonds (dashed lines).
3,3'-Dimethyl-1,1'-methylenediimidazolium dibromide top
Crystal data top
C9H14N42+·2BrF(000) = 332
Mr = 338.06Dx = 1.764 Mg m3
Monoclinic, P21/mMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybCell parameters from 1657 reflections
a = 4.7310 (5) Åθ = 2.5–26.3°
b = 11.3861 (12) ŵ = 6.34 mm1
c = 11.8419 (15) ÅT = 298 K
β = 93.672 (1)°Block, colourless
V = 636.59 (12) Å30.32 × 0.10 × 0.07 mm
Z = 2
Data collection top
Bruker SMART
diffractometer
1188 independent reflections
Radiation source: fine-focus sealed tube928 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.031
ϕ and ω scansθmax = 25.0°, θmin = 1.7°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 55
Tmin = 0.227, Tmax = 0.638k = 1310
3349 measured reflectionsl = 1413
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.028Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.066H-atom parameters constrained
S = 1.07 w = 1/[σ2(Fo2) + (0.0319P)2]
where P = (Fo2 + 2Fc2)/3
1188 reflections(Δ/σ)max < 0.001
74 parametersΔρmax = 0.63 e Å3
0 restraintsΔρmin = 0.27 e Å3
Crystal data top
C9H14N42+·2BrV = 636.59 (12) Å3
Mr = 338.06Z = 2
Monoclinic, P21/mMo Kα radiation
a = 4.7310 (5) ŵ = 6.34 mm1
b = 11.3861 (12) ÅT = 298 K
c = 11.8419 (15) Å0.32 × 0.10 × 0.07 mm
β = 93.672 (1)°
Data collection top
Bruker SMART
diffractometer
1188 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
928 reflections with I > 2σ(I)
Tmin = 0.227, Tmax = 0.638Rint = 0.031
3349 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0280 restraints
wR(F2) = 0.066H-atom parameters constrained
S = 1.07Δρmax = 0.63 e Å3
1188 reflectionsΔρmin = 0.27 e Å3
74 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Br10.14906 (11)0.75000.12842 (4)0.04708 (18)
Br20.86811 (10)0.25000.43062 (4)0.04621 (18)
N10.3731 (5)0.3553 (2)0.18410 (19)0.0333 (6)
N20.5612 (5)0.5023 (2)0.2736 (2)0.0375 (6)
C10.2048 (10)0.25000.1615 (4)0.0410 (11)
H1A0.13190.25000.08310.049*
H1B0.04470.25000.20880.049*
C20.3825 (7)0.4151 (3)0.2809 (2)0.0361 (8)
H20.27960.39780.34310.043*
C30.6745 (7)0.4977 (3)0.1702 (3)0.0450 (8)
H30.80810.54900.14360.054*
C40.5580 (7)0.4061 (3)0.1145 (3)0.0421 (8)
H40.59530.38140.04210.050*
C50.6396 (9)0.5872 (3)0.3625 (3)0.0699 (13)
H5A0.47420.62960.38200.105*
H5B0.77640.64120.33600.105*
H5C0.71970.54660.42800.105*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br10.0526 (4)0.0461 (3)0.0433 (3)0.0000.0087 (2)0.000
Br20.0433 (3)0.0484 (3)0.0471 (3)0.0000.0040 (2)0.000
N10.0389 (16)0.0264 (14)0.0339 (14)0.0034 (12)0.0035 (12)0.0049 (12)
N20.0483 (17)0.0230 (14)0.0405 (15)0.0001 (14)0.0022 (13)0.0011 (12)
C10.041 (3)0.037 (3)0.043 (3)0.0000.008 (2)0.000
C20.043 (2)0.0321 (18)0.0327 (16)0.0052 (16)0.0014 (14)0.0011 (14)
C30.053 (2)0.0311 (18)0.051 (2)0.0003 (17)0.0103 (17)0.0093 (17)
C40.055 (2)0.0358 (18)0.0355 (17)0.0082 (17)0.0063 (16)0.0059 (16)
C50.109 (4)0.042 (2)0.058 (3)0.019 (2)0.003 (2)0.0142 (19)
Geometric parameters (Å, º) top
N1—C21.331 (3)C1—H1B0.9700
N1—C41.368 (4)C2—H20.9300
N1—C11.455 (4)C3—C41.334 (4)
N2—C21.311 (4)C3—H30.9300
N2—C31.370 (4)C4—H40.9300
N2—C51.459 (4)C5—H5A0.9600
C1—N1i1.455 (4)C5—H5B0.9600
C1—H1A0.9700C5—H5C0.9600
C2—N1—C4108.4 (3)N1—C2—H2125.8
C2—N1—C1124.6 (3)C4—C3—N2107.4 (3)
C4—N1—C1127.0 (3)C4—C3—H3126.3
C2—N2—C3108.7 (3)N2—C3—H3126.3
C2—N2—C5126.1 (3)C3—C4—N1107.0 (3)
C3—N2—C5125.1 (3)C3—C4—H4126.5
N1—C1—N1i111.0 (4)N1—C4—H4126.5
N1—C1—H1A109.4N2—C5—H5A109.5
N1i—C1—H1A109.4N2—C5—H5B109.5
N1—C1—H1B109.4H5A—C5—H5B109.5
N1i—C1—H1B109.4N2—C5—H5C109.5
H1A—C1—H1B108.0H5A—C5—H5C109.5
N2—C2—N1108.5 (3)H5B—C5—H5C109.5
N2—C2—H2125.8
C2—N1—C1—N1i95.4 (4)C2—N2—C3—C40.6 (4)
C4—N1—C1—N1i80.7 (4)C5—N2—C3—C4177.6 (3)
C3—N2—C2—N11.1 (3)N2—C3—C4—N10.2 (4)
C5—N2—C2—N1178.2 (3)C2—N1—C4—C30.9 (4)
C4—N1—C2—N21.2 (3)C1—N1—C4—C3177.5 (3)
C1—N1—C2—N2177.9 (3)
Symmetry code: (i) x, y+1/2, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C4—H4···Br1ii0.932.843.724 (3)158
C3—H3···Br1iii0.932.813.699 (3)160
C1—H1A···Br1iv0.972.763.723 (4)172
C2—H2···Br2v0.932.823.627 (3)146
C1—H1B···Br2v0.972.813.652 (5)146
Symmetry codes: (ii) x+1, y+1, z; (iii) x+1, y, z; (iv) x, y+1, z; (v) x1, y, z.

Experimental details

Crystal data
Chemical formulaC9H14N42+·2Br
Mr338.06
Crystal system, space groupMonoclinic, P21/m
Temperature (K)298
a, b, c (Å)4.7310 (5), 11.3861 (12), 11.8419 (15)
β (°) 93.672 (1)
V3)636.59 (12)
Z2
Radiation typeMo Kα
µ (mm1)6.34
Crystal size (mm)0.32 × 0.10 × 0.07
Data collection
DiffractometerBruker SMART
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.227, 0.638
No. of measured, independent and
observed [I > 2σ(I)] reflections
3349, 1188, 928
Rint0.031
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.028, 0.066, 1.07
No. of reflections1188
No. of parameters74
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.63, 0.27

Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C4—H4···Br1i0.932.843.724 (3)158.1
C3—H3···Br1ii0.932.813.699 (3)159.6
C1—H1A···Br1iii0.972.763.723 (4)172.0
C2—H2···Br2iv0.932.823.627 (3)145.7
C1—H1B···Br2iv0.972.813.652 (5)146.1
Symmetry codes: (i) x+1, y+1, z; (ii) x+1, y, z; (iii) x, y+1, z; (iv) x1, y, z.
 

Acknowledgements

We acknowledge financial support by the National Natural Science Foundation of China (20773081, 20873074) and the National Basic Research Program (2007CB808004, 2009CB30101).

References

First citationEicher, T., Hauptmann, S. & Speicher, A. (2003). The Chemistry of Heterocycles: Structures, Reactions, Synthesis and Applications, 2th ed. Weinheim: Wiley-VCH.  Google Scholar
First citationJin, H.-S., Wang, H.-J., Zhang, Y., Zuo, Y.-J. & Zhong, C.-M. (2007). Acta Cryst. E63, o1880–o1881.  Web of Science CSD CrossRef IUCr Journals Google Scholar
First citationSheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.  Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationSiemens (1996). SMART and SAINT. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.  Google Scholar

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