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

Subramaniam, P.; Alias, Y.; Chandrasekaram, K.

doi:10.1107/S1600536810033490

organic compounds

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Volume 66| Part 9| September 2010| Page o2455

https://doi.org/10.1107/S1600536810033490

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

Puvaneswary Subramaniam,^a ^* Yatimah Alias ^a and Kumuthini Chandrasekaram ^a

^aDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: puvanes5881@yahoo.com

(Received 16 August 2010; accepted 19 August 2010; online 28 August 2010)

In the solid form of the title imidazolium-based ionic liquid salt, C₁₈H₂₄N₄²⁺·2CF₃SO₃⁻, the complete cation is generated by a crystallographic inversion centre. The five-membered imidazole ring is approximately perpendicular to the six-membered phenylene ring [dihedral angle = 85.11 (11)°]. In the crystal, the components are linked by C—H⋯O interactions.

Related literature

For background to imidazolium-based ionic liquid salts, see: Ganesan et al. (2008 ); Puvaneswary et al. (2009a ,b ,c ).

Experimental

Crystal data

C₁₈H₂₄N₄²⁺·2CF₃O₃S⁻
M_r = 594.55
Triclinic, $[P \overline 1]$
a = 7.3054 (1) Å
b = 8.0645 (2) Å
c = 11.3548 (2) Å
α = 89.946 (1)°
β = 76.653 (1)°
γ = 75.213 (1)°
V = 628.14 (2) Å³
Z = 1
Mo Kα radiation
μ = 0.30 mm⁻¹
T = 100 K
0.31 × 0.19 × 0.04 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.912, T_max = 0.988
5105 measured reflections
2273 independent reflections
1982 reflections with I > 2σ(I)
R_int = 0.021

Refinement

R[F² > 2σ(F²)] = 0.042
wR(F²) = 0.103
S = 1.16
2273 reflections
174 parameters
H-atom parameters constrained
Δρ_max = 0.33 e Å⁻³
Δρ_min = −0.37 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C6—H6A⋯O2ⁱ	0.99	2.35	3.251 (3)	152
C3—H3A⋯O2ⁱⁱ	0.98	2.59	3.424 (4)	144
C1—H1C⋯O2ⁱⁱ	0.98	2.49	3.296 (3)	139
C1—H1B⋯O1ⁱⁱⁱ	0.98	2.36	3.293 (3)	159
C1—H1A⋯O1^iv	0.98	2.52	3.164 (3)	123
Symmetry codes: (i) -x+2, -y, -z+1; (ii) -x+1, -y, -z+1; (iii) x-1, y, z; (iv) -x+1, -y+1, -z+1.

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, 2010 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536810033490/hg2702sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810033490/hg2702Isup2.hkl

checkCIF report

Comment top

Crystal structures of similar symmetrical compunds have been reported from our previous studies (Ganesan, et al., 2008; Puvaneswary et al., 2009a; 2009b; 2009c). As part of our ongoing research into imidazolium-based ionic liquids, we have synthesized 1,1',2,2'-tetramethyl-3,3'-(p-phenylenedimethylene)diimidazolium salt with trifluoromethanesulfonate anion.

The neighbouring cations in the title compund are held together via C–H···O hydrogen bonds in opposite directions through imidazole rings to CF₃SO₃^-anions and these hydrogen bonds stabilize the crystal structure.

Related literature top

For background to imidazolium-based ionic liquid salts, see: Ganesan et al. (2008); Puvaneswary et al. (2009a,b,c).

Experimental top

α,α-Dibromo-p-xylene (1.26 g, 4.77 mmol) and 1,2-dimethylimidazole (0.96 g, 9.99 mmol) were refluxed in DMF (50 ml) for 3 h. The product that separated from solution was collected and washed with ether. Crystals of the bromide salt were grown from its solution in water (Puvaneswary et al., 2009a).

The bromide salt (0.50 g, 1.10 mmol) and lithium trifluoromethanesulfonate (0.36 g, 2.31 mmol) were stirred in water (100 ml) for 24 h. Colourless crystals were obtained by slow evaporation of the solution (Melting point: 92–94°C).

Structure description top

For background to imidazolium-based ionic liquid salts, see: Ganesan et al. (2008); Puvaneswary et al. (2009a,b,c).

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); 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, 2010).

Figures top

Fig. 1. Thermal ellipsoid plot of the title compund at the 50% probability level. H atoms are drawn as spheres of arbitrary radius.

1,1',2,2'-Tetramethyl-3,3'-(p-phenylenedimethylene)diimidazol-1-ium bis(trifluoromethanesulfonate) top

Crystal data top

C₁₈H₂₄N₄²⁺·2CF₃O₃S⁻	Z = 1
M_r = 594.55	F(000) = 306
Triclinic, P1	D_x = 1.572 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.3054 (1) Å	Cell parameters from 1992 reflections
b = 8.0645 (2) Å	θ = 2.6–29.0°
c = 11.3548 (2) Å	µ = 0.30 mm⁻¹
α = 89.946 (1)°	T = 100 K
β = 76.653 (1)°	Plate, colourless
γ = 75.213 (1)°	0.31 × 0.19 × 0.04 mm
V = 628.14 (2) Å³

Data collection top

Bruker APEXII CCD diffractometer	2273 independent reflections
Radiation source: fine-focus sealed tube	1982 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.021
φ and ω scans	θ_max = 25.3°, θ_min = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −8→8
T_min = 0.912, T_max = 0.988	k = −9→9
5105 measured reflections	l = −13→13

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)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.103	H-atom parameters constrained
S = 1.16	w = 1/[σ²(F_o²) + (0.0241P)² + 1.0056P] where P = (F_o² + 2F_c²)/3
2273 reflections	(Δ/σ)_max < 0.001
174 parameters	Δρ_max = 0.33 e Å⁻³
0 restraints	Δρ_min = −0.37 e Å⁻³

Crystal data top

C₁₈H₂₄N₄²⁺·2CF₃O₃S⁻	γ = 75.213 (1)°
M_r = 594.55	V = 628.14 (2) Å³
Triclinic, P1	Z = 1
a = 7.3054 (1) Å	Mo Kα radiation
b = 8.0645 (2) Å	µ = 0.30 mm⁻¹
c = 11.3548 (2) Å	T = 100 K
α = 89.946 (1)°	0.31 × 0.19 × 0.04 mm
β = 76.653 (1)°

Data collection top

Bruker APEXII CCD diffractometer	2273 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1982 reflections with I > 2σ(I)
T_min = 0.912, T_max = 0.988	R_int = 0.021
5105 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.042	0 restraints
wR(F²) = 0.103	H-atom parameters constrained
S = 1.16	Δρ_max = 0.33 e Å⁻³
2273 reflections	Δρ_min = −0.37 e Å⁻³
174 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
N1	0.1441 (3)	0.2762 (3)	0.18655 (19)	0.0160 (5)
N2	0.3402 (3)	0.2113 (3)	0.30441 (19)	0.0154 (5)
C1	−0.0172 (4)	0.3018 (3)	0.4080 (2)	0.0184 (6)
H1A	−0.1168	0.4026	0.3949	0.028*
H1B	0.0251	0.3241	0.4810	0.028*
H1C	−0.0718	0.2022	0.4184	0.028*
C2	0.1513 (4)	0.2664 (3)	0.3023 (2)	0.0153 (5)
C3	−0.0369 (4)	0.3301 (4)	0.1445 (3)	0.0214 (6)
H3A	−0.1169	0.2498	0.1703	0.032*
H3B	−0.0050	0.3304	0.0558	0.032*
H3C	−0.1093	0.4459	0.1793	0.032*
C4	0.3304 (4)	0.2260 (3)	0.1129 (2)	0.0192 (6)
H4	0.3651	0.2214	0.0268	0.023*
C5	0.4525 (4)	0.1851 (3)	0.1863 (2)	0.0191 (6)
H5	0.5906	0.1454	0.1620	0.023*
C6	0.4164 (4)	0.1924 (3)	0.4137 (2)	0.0165 (6)
H6A	0.5389	0.0992	0.3970	0.020*
H6B	0.3214	0.1575	0.4796	0.020*
C7	0.4564 (3)	0.3550 (3)	0.4568 (2)	0.0144 (5)
C8	0.4553 (4)	0.4977 (3)	0.3878 (2)	0.0166 (6)
H8	0.4247	0.4974	0.3109	0.020*
C9	0.5011 (4)	0.3589 (3)	0.5692 (2)	0.0155 (5)
H9	0.5018	0.2624	0.6173	0.019*
S1	1.07181 (10)	0.18928 (9)	0.76648 (6)	0.01802 (18)
F1	0.7150 (2)	0.1636 (2)	0.78601 (16)	0.0331 (4)
F2	0.7393 (2)	0.3543 (2)	0.91048 (16)	0.0334 (4)
F3	0.8292 (2)	0.0858 (2)	0.94182 (14)	0.0272 (4)
O1	1.0372 (3)	0.3265 (3)	0.68688 (17)	0.0283 (5)
O2	1.1362 (3)	0.0188 (3)	0.70802 (19)	0.0332 (5)
O3	1.1741 (3)	0.2164 (3)	0.85592 (18)	0.0262 (5)
C10	0.8268 (4)	0.1991 (3)	0.8556 (2)	0.0204 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0189 (12)	0.0156 (11)	0.0150 (11)	−0.0052 (9)	−0.0060 (9)	−0.0006 (9)
N2	0.0154 (11)	0.0174 (12)	0.0136 (11)	−0.0046 (9)	−0.0035 (9)	0.0001 (9)
C1	0.0180 (14)	0.0191 (14)	0.0177 (13)	−0.0044 (11)	−0.0039 (11)	0.0009 (11)
C2	0.0188 (13)	0.0130 (13)	0.0162 (13)	−0.0063 (11)	−0.0059 (11)	0.0002 (10)
C3	0.0221 (15)	0.0233 (15)	0.0215 (14)	−0.0053 (12)	−0.0111 (12)	0.0003 (11)
C4	0.0247 (15)	0.0190 (14)	0.0136 (13)	−0.0081 (12)	−0.0009 (11)	−0.0017 (10)
C5	0.0173 (14)	0.0215 (14)	0.0174 (14)	−0.0062 (11)	−0.0007 (11)	−0.0032 (11)
C6	0.0160 (13)	0.0192 (14)	0.0157 (13)	−0.0050 (11)	−0.0060 (10)	0.0020 (10)
C7	0.0073 (12)	0.0192 (13)	0.0151 (13)	−0.0022 (10)	−0.0011 (10)	−0.0011 (10)
C8	0.0150 (13)	0.0227 (14)	0.0123 (12)	−0.0038 (11)	−0.0047 (10)	0.0009 (10)
C9	0.0131 (13)	0.0171 (13)	0.0155 (13)	−0.0022 (10)	−0.0041 (10)	0.0029 (10)
S1	0.0180 (4)	0.0213 (4)	0.0143 (3)	−0.0061 (3)	−0.0019 (3)	−0.0007 (3)
F1	0.0283 (10)	0.0448 (11)	0.0367 (10)	−0.0189 (8)	−0.0182 (8)	0.0115 (8)
F2	0.0254 (9)	0.0241 (9)	0.0409 (11)	0.0004 (7)	0.0038 (8)	−0.0048 (8)
F3	0.0329 (10)	0.0300 (9)	0.0213 (9)	−0.0150 (8)	−0.0044 (7)	0.0088 (7)
O1	0.0382 (12)	0.0340 (12)	0.0190 (10)	−0.0182 (10)	−0.0098 (9)	0.0098 (9)
O2	0.0293 (12)	0.0287 (12)	0.0355 (13)	−0.0059 (9)	0.0024 (10)	−0.0137 (10)
O3	0.0222 (11)	0.0357 (12)	0.0227 (11)	−0.0089 (9)	−0.0081 (8)	0.0034 (9)
C10	0.0216 (15)	0.0187 (14)	0.0209 (14)	−0.0047 (11)	−0.0060 (12)	0.0023 (11)

Geometric parameters (Å, º) top

N1—C2	1.329 (3)	C6—C7	1.520 (4)
N1—C4	1.382 (3)	C6—H6A	0.9900
N1—C3	1.471 (3)	C6—H6B	0.9900
N2—C2	1.343 (3)	C7—C9	1.390 (4)
N2—C5	1.386 (3)	C7—C8	1.391 (4)
N2—C6	1.466 (3)	C8—C9ⁱ	1.392 (4)
C1—C2	1.475 (4)	C8—H8	0.9500
C1—H1A	0.9800	C9—C8ⁱ	1.392 (4)
C1—H1B	0.9800	C9—H9	0.9500
C1—H1C	0.9800	S1—O1	1.438 (2)
C3—H3A	0.9800	S1—O3	1.439 (2)
C3—H3B	0.9800	S1—O2	1.442 (2)
C3—H3C	0.9800	S1—C10	1.824 (3)
C4—C5	1.339 (4)	F1—C10	1.338 (3)
C4—H4	0.9500	F2—C10	1.331 (3)
C5—H5	0.9500	F3—C10	1.338 (3)

C2—N1—C4	109.9 (2)	N2—C6—C7	113.6 (2)
C2—N1—C3	124.5 (2)	N2—C6—H6A	108.8
C4—N1—C3	125.6 (2)	C7—C6—H6A	108.8
C2—N2—C5	109.0 (2)	N2—C6—H6B	108.8
C2—N2—C6	125.6 (2)	C7—C6—H6B	108.8
C5—N2—C6	125.3 (2)	H6A—C6—H6B	107.7
C2—C1—H1A	109.5	C9—C7—C8	118.8 (2)
C2—C1—H1B	109.5	C9—C7—C6	118.2 (2)
H1A—C1—H1B	109.5	C8—C7—C6	123.0 (2)
C2—C1—H1C	109.5	C7—C8—C9ⁱ	120.3 (2)
H1A—C1—H1C	109.5	C7—C8—H8	119.8
H1B—C1—H1C	109.5	C9ⁱ—C8—H8	119.8
N1—C2—N2	107.0 (2)	C7—C9—C8ⁱ	120.9 (2)
N1—C2—C1	126.3 (2)	C7—C9—H9	119.5
N2—C2—C1	126.6 (2)	C8ⁱ—C9—H9	119.5
N1—C3—H3A	109.5	O1—S1—O3	115.23 (12)
N1—C3—H3B	109.5	O1—S1—O2	115.05 (13)
H3A—C3—H3B	109.5	O3—S1—O2	114.61 (13)
N1—C3—H3C	109.5	O1—S1—C10	102.57 (13)
H3A—C3—H3C	109.5	O3—S1—C10	103.71 (12)
H3B—C3—H3C	109.5	O2—S1—C10	103.25 (13)
C5—C4—N1	106.8 (2)	F2—C10—F3	107.4 (2)
C5—C4—H4	126.6	F2—C10—F1	107.8 (2)
N1—C4—H4	126.6	F3—C10—F1	107.1 (2)
C4—C5—N2	107.3 (2)	F2—C10—S1	111.33 (19)
C4—C5—H5	126.4	F3—C10—S1	111.72 (19)
N2—C5—H5	126.4	F1—C10—S1	111.34 (19)

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
C6—H6A···O2ⁱⁱ	0.99	2.35	3.251 (3)	152
C3—H3A···O2ⁱⁱⁱ	0.98	2.59	3.424 (4)	144
C1—H1C···O2ⁱⁱⁱ	0.98	2.49	3.296 (3)	139
C1—H1B···O1^iv	0.98	2.36	3.293 (3)	159
C1—H1A···O1ⁱ	0.98	2.52	3.164 (3)	123

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+2, −y, −z+1; (iii) −x+1, −y, −z+1; (iv) x−1, y, z.

Experimental details

Crystal data
Chemical formula	C₁₈H₂₄N₄²⁺·2CF₃O₃S⁻
M_r	594.55
Crystal system, space group	Triclinic, P1
Temperature (K)	100
a, b, c (Å)	7.3054 (1), 8.0645 (2), 11.3548 (2)
α, β, γ (°)	89.946 (1), 76.653 (1), 75.213 (1)
V (Å³)	628.14 (2)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	0.30
Crystal size (mm)	0.31 × 0.19 × 0.04

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.912, 0.988
No. of measured, independent and observed [I > 2σ(I)] reflections	5105, 2273, 1982
R_int	0.021
(sin θ/λ)_max (Å⁻¹)	0.600

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.103, 1.16
No. of reflections	2273
No. of parameters	174
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.33, −0.37

Computer programs: APEX2 (Bruker, 2008), SAINT (Bruker, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6A···O2ⁱ	0.99	2.35	3.251 (3)	151.6
C3—H3A···O2ⁱⁱ	0.98	2.59	3.424 (4)	143.6
C1—H1C···O2ⁱⁱ	0.98	2.49	3.296 (3)	139.2
C1—H1B···O1ⁱⁱⁱ	0.98	2.36	3.293 (3)	158.8
C1—H1A···O1^iv	0.98	2.52	3.164 (3)	122.8

Symmetry codes: (i) −x+2, −y, −z+1; (ii) −x+1, −y, −z+1; (iii) x−1, y, z; (iv) −x+1, −y+1, −z+1.

Acknowledgements

The authors would like to thank the University of Malaya for the financial support (grant Nos. RG062–09SUS and TA021–2009A).

References

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

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