1,1′,2,2′-Tetra­methyl-3,3′-(p-phenyl­enedimethyl­ene)diimidazol-1-ium dibromide

Subramaniam Puvaneswary; Yatimah Alias; Seik Weng Ng

doi:10.1107/S1600536809026324

. 2009 Jul 11;65(Pt 8):o1828. doi: 10.1107/S1600536809026324

1,1′,2,2′-Tetramethyl-3,3′-(p-phenylenedimethylene)diimidazol-1-ium dibromide

Subramaniam Puvaneswary ^a, Yatimah Alias ^a, Seik Weng Ng ^a,^*

PMCID: PMC2977381 PMID: 21583530

Abstract

The title imidazolium-based ionic-liquid salt, C₁₈H₂₄N₄ ²⁺·2Br⁻, has the cation lying about a center of inversion. The five-membered imidazole ring is disordered over two positions with the major component having a site occupancy of 0.712 (4); the N-bound methyl substituents are ordered. The imidazole ring is approximately perpendicular to the six-membered phenylene ring [dihedral angle = 80.7 (5)° for the major disorder component and 89.8 (3)° for the other; the two components are off-set by 10.1 (6)°].

Related literature

For background to imidazolium-based ionic liquid salts, see: Ganesan et al. (2008 ▶). For 2,2′-dimethyl-3,3′-(p-phenylenedimethylene)diimidazol-1-ium dibromide, see: Dobrzańska (2005 ▶).

Experimental

Crystal data

C₁₈H₂₄N₄ ²⁺·2Br⁻
M _r = 456.23
Monoclinic,
a = 8.5689 (4) Å
b = 9.8617 (5) Å
c = 11.0272 (4) Å
β = 93.222 (3)°
V = 930.37 (7) Å³
Z = 2
Mo Kα radiation
μ = 4.36 mm⁻¹
T = 140 K
0.40 × 0.08 × 0.04 mm

Data collection

Bruker SMART APEX diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.274, T _max = 0.845
5882 measured reflections
2131 independent reflections
1575 reflections with I > 2σ(I)
R _int = 0.051

Refinement

R[F ² > 2σ(F ²)] = 0.039
wR(F ²) = 0.096
S = 1.04
2131 reflections
112 parameters
36 restraints
H-atom parameters constrained
Δρ_max = 0.54 e Å⁻³
Δρ_min = −0.99 e Å⁻³

Data collection: APEX2 (Bruker, 2008 ▶); cell refinement: SAINT (Bruker, 2008 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: X-SEED (Barbour, 2001 ▶); software used to prepare material for publication: publCIF (Westrip, 2009 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809026324/tk2494sup1.cif

e-65-o1828-sup1.cif^{(17.2KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809026324/tk2494Isup2.hkl

e-65-o1828-Isup2.hkl^{(104.8KB, hkl)}

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

Acknowledgments

We thank the University of Malaya (grant Nos. TA 0009/2008 A and FS343/2008 A) for supporting this study.

supplementary crystallographic information

Experimental

α,α-Dibromo-p-xylene (0.78 g, 3 mmol) and 1,2-dimethylimidazole (0.58 g, 6 mmol) were refluxed in DMF (50 ml) for 3 h. The product that separated from solution was collected and washed with ether. Crystals were grown from its solution in water.

Figures

Fig. 1. — Thermal ellipsoid plot (Barbour, 2001) of [C18H24N4]2+ 2Br- at the 70% probability level; hydrogen atoms are drawn as spheres of arbitrary radius. The imidazolyl ring is disordered; the minor component of the disorder is not shown. The non-H atoms comprising the asymmetric unit are labelled and the unlabelled atoms are related by 1-x, -y, -z.

Crystal data

C₁₈H₂₄N₄²⁺·2Br⁻	F(000) = 460
M_r = 456.23	D_x = 1.629 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 1543 reflections
a = 8.5689 (4) Å	θ = 2.8–25.5°
b = 9.8617 (5) Å	µ = 4.36 mm⁻¹
c = 11.0272 (4) Å	T = 140 K
β = 93.222 (3)°	Prism, colorless
V = 930.37 (7) Å³	0.40 × 0.08 × 0.04 mm
Z = 2

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Data collection

Bruker SMART APEX diffractometer	2131 independent reflections
Radiation source: fine-focus sealed tube	1575 reflections with I > 2σ(I)
graphite	R_int = 0.051
ω scans	θ_max = 27.5°, θ_min = 2.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −11→10
T_min = 0.274, T_max = 0.845	k = −12→12
5882 measured reflections	l = −14→14

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Refinement

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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.096	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0403P)² + 0.5004P] where P = (F_o² + 2F_c²)/3
2131 reflections	(Δ/σ)_max = 0.001
112 parameters	Δρ_max = 0.54 e Å⁻³
36 restraints	Δρ_min = −0.99 e Å⁻³

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Br1	0.46792 (4)	0.59691 (4)	0.76873 (3)	0.02742 (14)
C1	0.6432 (4)	0.0488 (4)	0.4669 (3)	0.0194 (7)
H1	0.7414	0.0823	0.4445	0.023*
C2	0.6148 (4)	0.0331 (3)	0.5895 (3)	0.0194 (7)
H2	0.6936	0.0558	0.6501	0.023*
C3	0.4712 (4)	−0.0158 (3)	0.6230 (3)	0.0188 (7)
C4	0.4343 (4)	−0.0353 (4)	0.7539 (3)	0.0201 (7)
H4A	0.3204	−0.0246	0.7615	0.024*	0.712 (4)
H4B	0.4631	−0.1287	0.7794	0.024*	0.712 (4)
H4C	0.4003	−0.1303	0.7649	0.024*	0.288 (4)
H4D	0.3452	0.0241	0.7714	0.024*	0.288 (4)
N1	0.5158 (3)	0.0594 (3)	0.8328 (3)	0.0199 (10)	0.712 (4)
C5	0.4760 (4)	0.1910 (3)	0.8444 (3)	0.0259 (11)	0.712 (4)
H5	0.3862	0.2336	0.8072	0.031*	0.712 (4)
C6	0.5862 (4)	0.2513 (2)	0.9182 (3)	0.0270 (13)	0.712 (4)
H6	0.5875	0.3439	0.9421	0.032*	0.712 (4)
N2	0.6941 (3)	0.1570 (3)	0.9523 (3)	0.0207 (9)	0.712 (4)
C7	0.6507 (4)	0.0384 (2)	0.8994 (3)	0.0203 (11)	0.712 (4)
C8	0.7408 (7)	−0.0908 (5)	0.9105 (5)	0.0256 (12)	0.712 (4)
H8A	0.8262	−0.0889	0.8549	0.038*	0.712 (4)
H8B	0.6714	−0.1673	0.8896	0.038*	0.712 (4)
H8C	0.7842	−0.1012	0.9941	0.038*	0.712 (4)
N1'	0.5677 (9)	−0.0057 (8)	0.8456 (6)	0.0199 (10)	0.288
C5'	0.6581 (11)	−0.1058 (6)	0.8950 (8)	0.0259 (11)	0.288
H5'	0.6480	−0.1998	0.8775	0.031*	0.288 (4)
C6'	0.7654 (9)	−0.0488 (8)	0.9736 (8)	0.0270 (13)	0.288
H6'	0.8440	−0.0956	1.0211	0.032*	0.288 (4)
N2'	0.7413 (9)	0.0865 (7)	0.9728 (7)	0.0207 (9)	0.288
C7'	0.6192 (10)	0.1132 (6)	0.8937 (7)	0.0203 (11)	0.288
C8'	0.5509 (19)	0.2515 (14)	0.8644 (14)	0.0256 (12)	0.288
H8'1	0.5473	0.3048	0.9392	0.038*	0.288 (4)
H8'2	0.4448	0.2412	0.8275	0.038*	0.288 (4)
H8'3	0.6162	0.2983	0.8074	0.038*	0.288 (4)
C9	0.8342 (5)	0.1840 (4)	1.0313 (3)	0.0293 (9)
H9A	0.8278	0.2755	1.0654	0.044*	0.712 (4)
H9B	0.9272	0.1770	0.9840	0.044*	0.712 (4)
H9C	0.8410	0.1175	1.0975	0.044*	0.712 (4)
H9D	0.7798	0.2715	1.0279	0.044*	0.288 (4)
H9E	0.9330	0.1919	0.9912	0.044*	0.288 (4)
H9F	0.8555	0.1577	1.1164	0.044*	0.288 (4)

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Atomic displacement parameters (Å²)

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0221 (2)	0.0266 (2)	0.0336 (2)	0.00039 (17)	0.00258 (14)	−0.00512 (16)
C1	0.0122 (19)	0.0253 (17)	0.0208 (17)	−0.0017 (14)	0.0021 (13)	0.0009 (13)
C2	0.016 (2)	0.0235 (18)	0.0183 (17)	0.0002 (14)	−0.0025 (13)	−0.0002 (13)
C3	0.019 (2)	0.0188 (17)	0.0192 (17)	0.0022 (14)	0.0025 (13)	0.0007 (13)
C4	0.013 (2)	0.0275 (18)	0.0194 (17)	−0.0009 (14)	−0.0008 (13)	0.0010 (13)
N1	0.018 (2)	0.025 (2)	0.0168 (18)	−0.0023 (17)	0.0016 (16)	0.0014 (17)
C5	0.025 (3)	0.030 (3)	0.022 (2)	0.008 (2)	0.000 (2)	0.000 (2)
C6	0.027 (3)	0.026 (3)	0.028 (3)	0.006 (2)	0.000 (2)	0.002 (2)
N2	0.020 (3)	0.025 (2)	0.0164 (19)	−0.0032 (18)	0.0019 (16)	0.0007 (17)
C7	0.018 (3)	0.023 (3)	0.021 (2)	0.000 (2)	0.0055 (18)	0.005 (2)
C8	0.021 (3)	0.021 (2)	0.034 (3)	0.009 (2)	0.000 (2)	0.012 (2)
N1'	0.018 (2)	0.025 (2)	0.0168 (18)	−0.0023 (17)	0.0016 (16)	0.0014 (17)
C5'	0.025 (3)	0.030 (3)	0.022 (2)	0.008 (2)	0.000 (2)	0.000 (2)
C6'	0.027 (3)	0.026 (3)	0.028 (3)	0.006 (2)	0.000 (2)	0.002 (2)
N2'	0.020 (3)	0.025 (2)	0.0164 (19)	−0.0032 (18)	0.0019 (16)	0.0007 (17)
C7'	0.018 (3)	0.023 (3)	0.021 (2)	0.000 (2)	0.0055 (18)	0.005 (2)
C8'	0.021 (3)	0.021 (2)	0.034 (3)	0.009 (2)	0.000 (2)	0.012 (2)
C9	0.025 (2)	0.034 (2)	0.027 (2)	−0.0067 (17)	−0.0061 (16)	0.0026 (16)

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Geometric parameters (Å, °)

C1—C3ⁱ	1.392 (5)	C8—H8A	0.9800
C1—C2	1.396 (4)	C8—H8B	0.9800
C1—H1	0.9500	C8—H8C	0.9800
C2—C3	1.391 (5)	N1'—C5'	1.3500
C2—H2	0.9500	N1'—C7'	1.3500
C3—C1ⁱ	1.392 (5)	C5'—C6'	1.3500
C3—C4	1.507 (4)	C5'—H5'	0.9500
C4—N1	1.432 (4)	C6'—N2'	1.3500
C4—N1'	1.512 (7)	C6'—H6'	0.9500
C4—H4A	0.9900	N2'—C7'	1.3500
C4—H4B	0.9900	N2'—C9	1.384 (7)
C4—H4C	0.9900	C7'—C8'	1.513 (15)
C4—H4D	0.9900	C8'—H8'1	0.9800
N1—C5	1.3500	C8'—H8'2	0.9800
N1—C7	1.3500	C8'—H8'3	0.9800
C5—C6	1.3500	C9—H9A	0.9800
C5—H5	0.9500	C9—H9B	0.9800
C6—N2	1.3500	C9—H9C	0.9800
C6—H6	0.9500	C9—H9D	0.9800
N2—C7	1.3500	C9—H9E	0.9800
N2—C9	1.468 (4)	C9—H9F	0.9800
C7—C8	1.492 (5)

C3ⁱ—C1—C2	120.6 (3)	N2—C7—C8	125.2 (3)
C3ⁱ—C1—H1	119.7	N1—C7—C8	126.8 (3)
C2—C1—H1	119.7	C5'—N1'—C7'	108.0
C3—C2—C1	120.1 (3)	C5'—N1'—C4	121.6 (6)
C3—C2—H2	120.0	C7'—N1'—C4	130.4 (6)
C1—C2—H2	120.0	C6'—C5'—N1'	108.0
C2—C3—C1ⁱ	119.3 (3)	C6'—C5'—H5'	126.0
C2—C3—C4	122.4 (3)	N1'—C5'—H5'	126.0
C1ⁱ—C3—C4	118.3 (3)	C5'—C6'—N2'	108.0
N1—C4—C3	112.1 (3)	C5'—C6'—H6'	126.0
C3—C4—N1'	115.1 (4)	N2'—C6'—H6'	126.0
N1—C4—H4A	109.2	C7'—N2'—C6'	108.0
C3—C4—H4A	109.2	C7'—N2'—C9	124.8 (6)
N1'—C4—H4A	129.4	C6'—N2'—C9	126.8 (6)
N1—C4—H4B	109.2	N2'—C7'—N1'	108.0
C3—C4—H4B	109.2	N2'—C7'—C8'	126.2 (8)
H4A—C4—H4B	107.9	N1'—C7'—C8'	125.8 (8)
C3—C4—H4C	108.5	C7'—C8'—H8'1	109.5
N1'—C4—H4C	108.5	C7'—C8'—H8'2	109.5
C3—C4—H4D	108.5	H8'1—C8'—H8'2	109.5
N1'—C4—H4D	108.5	C7'—C8'—H8'3	109.5
H4C—C4—H4D	107.5	H8'1—C8'—H8'3	109.5
C5—N1—C7	108.0	H8'2—C8'—H8'3	109.5
C5—N1—C4	124.6 (3)	N2—C9—H9A	109.5
C7—N1—C4	127.2 (3)	N2—C9—H9B	109.5
N1—C5—C6	108.0	H9A—C9—H9B	109.5
N1—C5—H5	126.0	N2—C9—H9C	109.5
C6—C5—H5	126.0	H9A—C9—H9C	109.5
N2—C6—C5	108.0	H9B—C9—H9C	109.5
N2—C6—H6	126.0	N2'—C9—H9D	109.5
C5—C6—H6	126.0	N2'—C9—H9E	109.5
C6—N2—C7	108.0	H9D—C9—H9E	109.5
C6—N2—C9	124.4 (3)	N2'—C9—H9F	109.5
C7—N2—C9	127.6 (3)	H9D—C9—H9F	109.5
N2—C7—N1	108.0	H9E—C9—H9F	109.5

C3ⁱ—C1—C2—C3	−0.1 (6)	C4—N1—C7—C8	−3.3 (5)
C1—C2—C3—C1ⁱ	0.1 (6)	N1—C4—N1'—C5'	170.1 (11)
C1—C2—C3—C4	179.8 (3)	C3—C4—N1'—C5'	−98.3 (6)
C2—C3—C4—N1	30.3 (5)	N1—C4—N1'—C7'	−9.2 (5)
C1ⁱ—C3—C4—N1	−150.0 (3)	C3—C4—N1'—C7'	82.4 (8)
C2—C3—C4—N1'	−3.4 (6)	C7'—N1'—C5'—C6'	0.0
C1ⁱ—C3—C4—N1'	176.3 (4)	C4—N1'—C5'—C6'	−179.5 (8)
C3—C4—N1—C5	76.5 (4)	N1'—C5'—C6'—N2'	0.0
N1'—C4—N1—C5	178.8 (8)	C5'—C6'—N2'—C7'	0.0
C3—C4—N1—C7	−97.3 (3)	C5'—C6'—N2'—C9	−173.4 (8)
N1'—C4—N1—C7	4.9 (7)	C6'—N2'—C7'—N1'	0.0
C7—N1—C5—C6	0.0	C9—N2'—C7'—N1'	173.5 (8)
C4—N1—C5—C6	−174.8 (3)	C6'—N2'—C7'—C8'	179.7 (11)
N1—C5—C6—N2	0.0	C9—N2'—C7'—C8'	−6.8 (12)
C5—C6—N2—C7	0.0	C5'—N1'—C7'—N2'	0.0
C5—C6—N2—C9	179.0 (3)	C4—N1'—C7'—N2'	179.4 (8)
C6—N2—C7—N1	0.0	C5'—N1'—C7'—C8'	−179.7 (11)
C9—N2—C7—N1	−179.0 (4)	C4—N1'—C7'—C8'	−0.3 (12)
C6—N2—C7—C8	178.0 (4)	C7'—N2'—C9—N2	6.6 (5)
C9—N2—C7—C8	−1.0 (5)	C6'—N2'—C9—N2	179.0 (11)
C5—N1—C7—N2	0.0	C6—N2—C9—N2'	171.4 (8)
C4—N1—C7—N2	174.7 (3)	C7—N2—C9—N2'	−9.8 (7)
C5—N1—C7—C8	−177.9 (4)

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Symmetry codes: (i) −x+1, −y, −z+1.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: TK2494).

References

Barbour, L. J. (2001). J. Supramol. Chem.1, 189–191.
Bruker (2008). APEX2 and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
Dobrzańska, L. (2005). Acta Cryst. E61, o4113–o4115.
Ganesan, K., Alias, Y. & Ng, S. W. (2008). Acta Cryst. C64, o478–o480. [DOI] [PubMed]
Sheldrick, G. M. (1996). SADABS University of Göttingen, Germany.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [DOI] [PubMed]
Westrip, S. P. (2009). publCIF In preparation.

Associated Data

This section collects any data citations, data availability statements, or supplementary materials included in this article.

Supplementary Materials

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809026324/tk2494sup1.cif

e-65-o1828-sup1.cif^{(17.2KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809026324/tk2494Isup2.hkl

e-65-o1828-Isup2.hkl^{(104.8KB, hkl)}

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

[bb1] Barbour, L. J. (2001). J. Supramol. Chem.1, 189–191.

[bb2] Bruker (2008). APEX2 and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.

[bb3] Dobrzańska, L. (2005). Acta Cryst. E61, o4113–o4115.

[bb4] Ganesan, K., Alias, Y. & Ng, S. W. (2008). Acta Cryst. C64, o478–o480. [DOI] [PubMed]

[bb5] Sheldrick, G. M. (1996). SADABS University of Göttingen, Germany.

[bb6] Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [DOI] [PubMed]

[bb7] Westrip, S. P. (2009). publCIF In preparation.

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1,1′,2,2′-Tetramethyl-3,3′-(p-phenylenedimethylene)diimidazol-1-ium dibromide

Subramaniam Puvaneswary

Yatimah Alias

Seik Weng Ng

Abstract

Related literature

Experimental

Crystal data

Data collection

Refinement

Supplementary Material

Acknowledgments

supplementary crystallographic information

Experimental

Refinement

Figures

Fig. 1.

Crystal data

Data collection

Refinement

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

Atomic displacement parameters (Å²)

Geometric parameters (Å, °)

Footnotes

References

Associated Data

Supplementary Materials

ACTIONS

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PERMALINK

1,1′,2,2′-Tetra­methyl-3,3′-(p-phenyl­enedimethyl­ene)diimidazol-1-ium dibromide

Subramaniam Puvaneswary

Yatimah Alias

Seik Weng Ng

Abstract

Related literature

Experimental

Crystal data

Data collection

Refinement

Supplementary Material

Acknowledgments

supplementary crystallographic information

Experimental

Refinement

Figures

Fig. 1.

Crystal data

Data collection

Refinement

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

Atomic displacement parameters (Å2)

Geometric parameters (Å, °)

Footnotes

References

Associated Data

Supplementary Materials

ACTIONS

PERMALINK

RESOURCES

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1,1′,2,2′-Tetramethyl-3,3′-(p-phenylenedimethylene)diimidazol-1-ium dibromide

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

Atomic displacement parameters (Å²)