1,1′,2,2′-Tetra­methyl-3,3′-(p-phenyl­ene­dimethyl­ene)diimidazol-1-ium bis­[bis­(trifluoro­methyl­sulfon­yl)imide]

Abdul Rahim, M.S.; Alias, Y.; Ng, S.W.

doi:10.1107/S1600536810038006

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 66| Part 10| October 2010| Page o2668

doi:10.1107/S1600536810038006

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1,1′,2,2′-Tetramethyl-3,3′-(p-phenylenedimethylene)diimidazol-1-ium bis[bis(trifluoromethylsulfonyl)imide]

Munirah Sufiyah Abdul Rahim,^a Yatimah Alias ^a and Seik Weng Ng ^a ^*

^aDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: seikweng@um.edu.my

(Received 9 September 2010; accepted 22 September 2010; online 30 September 2010)

The cation of the imidazolium-based ionic-liquid title salt, C₁₆H₂₄N₄²⁺·2C₂F₆NO₄S₂⁻, lies on a center of inversion; in the cation, the five-membered imidazolium ring is aligned at 84.4 (1)° with respect to the phenylene ring; the angle at the methylene C atom is 113.0 (2)°. In the anion, the negative charge formally resides on the two-coordinate N atom; the S—N—S angle at this atom is 125.2 (1)°.

Related literature

For the tetrafluoroborate and hexafluorophosphate salts, see: Puvaneswary et al. (2009a ,b ).

Experimental

Crystal data

C₁₆H₂₄N₄²⁺·2C₂F₆NO₄S₂⁻
M_r = 856.71
Monoclinic, P 2₁ /n
a = 8.7195 (7) Å
b = 13.710 (1) Å
c = 13.8351 (11) Å
β = 92.290 (1)°
V = 1652.6 (2) Å³
Z = 2
Mo Kα radiation
μ = 0.41 mm⁻¹
T = 100 K
0.40 × 0.30 × 0.20 mm

Data collection

Bruker SMART APEX diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.853, T_max = 0.922
10192 measured reflections
3744 independent reflections
3191 reflections with I > 2σ(I)
R_int = 0.023

Refinement

R[F² > 2σ(F²)] = 0.034
wR(F²) = 0.092
S = 1.02
3744 reflections
237 parameters
H-atom parameters constrained
Δρ_max = 0.48 e Å⁻³
Δρ_min = −0.41 e Å⁻³

Data collection: APEX2 (Bruker, 2009 ); cell refinement: SAINT (Bruker, 2009); 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 global, I. DOI: 10.1107/S1600536810038006/jh2208sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810038006/jh2208Isup2.hkl

checkCIF report

Comment top

We have previously reported 1,1',2,2'-tetramethyl-3,3'-(p-phenylenedimethylene)-bis(imidazol-1-ium) salts (Puvaneswary et al., 2009a, 2009b). Such compounds are ionic-liquid salts based on an imidazolium entity. The principal feauture of these salts is the non-nucleophilic nature of the counterion. The present bis(trifluoromethanesulfonyl)imide salt (Scheme I, Fig. 1) represents another example of such an anion. The cation lies on a center-of-inversion. The five-membered limidazolyl ring is aligned at with respect to the phenylene ring 84.4 (1) °; the angle at the methylene carbon is 113.0 (2) °. In the anion, the negative charge formally resides on the two-coordinate nitrogen; the angle at this atom is 125.2 (1) °.

Related literature top

For the tetrafluoroborate and hexafluorophosphate salts, see: Puvaneswary et al. (2009a,b).

Experimental top

1,1',2,2'-Tetramethyl-3,3'-(p-phenylenedimethylene)-bis(imidazol-1-ium) bromide (1 mmol) and lithium bis(trifluoromethanesulfonyl)imide (2 mmol) were mixed in water for 2 h to give a solid material. This was collected and recrystallized from ethyl acetate

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); 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 (Barbour, 2001) of C₁₆H₂₄N₄²⁺ 2C₂F₆NO₄S₂^- at the 70% probability level; hydrogen atoms are drawn as spheres of arbitrary radius. Symmetry-related atoms are not labeled.

1,1',2,2'-Tetramethyl-3,3'-(p-phenylenedimethylene)diimidazol-1-ium bis[bis(trifluoromethylsulfonyl)imide] top

Crystal data top

C₁₆H₂₄N₄²⁺·2C₂F₆NO₄S₂⁻	F(000) = 868
M_r = 856.71	D_x = 1.722 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 4645 reflections
a = 8.7195 (7) Å	θ = 2.7–28.4°
b = 13.710 (1) Å	µ = 0.41 mm⁻¹
c = 13.8351 (11) Å	T = 100 K
β = 92.290 (1)°	Block, colorless
V = 1652.6 (2) Å³	0.40 × 0.30 × 0.20 mm
Z = 2

Data collection top

Bruker SMART APEX diffractometer	3744 independent reflections
Radiation source: fine-focus sealed tube	3191 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.023
ω scans	θ_max = 27.5°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −11→11
T_min = 0.853, T_max = 0.922	k = −14→17
10192 measured reflections	l = −15→17

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)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.092	H-atom parameters constrained
S = 1.02	w = 1/[σ²(F_o²) + (0.042P)² + 1.3932P] where P = (F_o² + 2F_c²)/3
3744 reflections	(Δ/σ)_max = 0.001
237 parameters	Δρ_max = 0.48 e Å⁻³
0 restraints	Δρ_min = −0.41 e Å⁻³

Crystal data top

C₁₆H₂₄N₄²⁺·2C₂F₆NO₄S₂⁻	V = 1652.6 (2) Å³
M_r = 856.71	Z = 2
Monoclinic, P2₁/n	Mo Kα radiation
a = 8.7195 (7) Å	µ = 0.41 mm⁻¹
b = 13.710 (1) Å	T = 100 K
c = 13.8351 (11) Å	0.40 × 0.30 × 0.20 mm
β = 92.290 (1)°

Data collection top

Bruker SMART APEX diffractometer	3744 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	3191 reflections with I > 2σ(I)
T_min = 0.853, T_max = 0.922	R_int = 0.023
10192 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	0 restraints
wR(F²) = 0.092	H-atom parameters constrained
S = 1.02	Δρ_max = 0.48 e Å⁻³
3744 reflections	Δρ_min = −0.41 e Å⁻³
237 parameters

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

	x	y	z	U_iso*/U_eq
S1	0.67739 (5)	0.67845 (3)	0.91285 (3)	0.01904 (12)
S2	0.38200 (5)	0.75917 (3)	0.90601 (3)	0.01821 (12)
F1	0.71875 (14)	0.85090 (8)	0.83605 (9)	0.0308 (3)
F2	0.76447 (14)	0.73079 (9)	0.74157 (8)	0.0300 (3)
F3	0.92506 (13)	0.76619 (10)	0.85879 (10)	0.0390 (3)
F4	0.21558 (15)	0.60557 (10)	0.94569 (9)	0.0361 (3)
F5	0.15962 (13)	0.73471 (9)	1.02456 (9)	0.0308 (3)
F6	0.36490 (15)	0.65461 (10)	1.06344 (8)	0.0347 (3)
O1	0.73759 (16)	0.58470 (11)	0.89041 (11)	0.0289 (3)
O2	0.70581 (15)	0.71643 (11)	1.00822 (10)	0.0272 (3)
O3	0.27597 (15)	0.77674 (11)	0.82658 (10)	0.0277 (3)
O4	0.43736 (15)	0.83923 (10)	0.96315 (10)	0.0267 (3)
N1	0.09231 (18)	0.48286 (12)	0.77903 (11)	0.0211 (3)
N2	0.23507 (18)	0.57396 (12)	0.69354 (11)	0.0208 (3)
N3	0.50715 (17)	0.68460 (12)	0.87134 (11)	0.0196 (3)
C1	0.4064 (2)	0.45239 (15)	0.43276 (13)	0.0215 (4)
H1	0.3417	0.4197	0.3863	0.026*
C2	0.3415 (2)	0.50636 (15)	0.50513 (13)	0.0219 (4)
H2	0.2331	0.5103	0.5084	0.026*
C3	0.4355 (2)	0.55475 (13)	0.57304 (12)	0.0170 (4)
C4	0.3691 (2)	0.61775 (14)	0.65040 (13)	0.0210 (4)
H4A	0.4490	0.6297	0.7019	0.025*
H4B	0.3394	0.6816	0.6219	0.025*
C5	0.0846 (2)	0.60245 (16)	0.67350 (14)	0.0261 (4)
H5	0.0510	0.6527	0.6304	0.031*
C6	−0.0041 (2)	0.54552 (15)	0.72652 (14)	0.0254 (4)
H6	−0.1128	0.5476	0.7279	0.030*
C7	0.0391 (2)	0.41044 (15)	0.84840 (14)	0.0242 (4)
H7A	0.1006	0.4157	0.9090	0.036*
H7B	0.0503	0.3448	0.8215	0.036*
H7C	−0.0690	0.4225	0.8610	0.036*
C8	0.2373 (2)	0.50107 (14)	0.75707 (12)	0.0189 (4)
C9	0.3763 (2)	0.45077 (15)	0.79565 (14)	0.0239 (4)
H9A	0.4512	0.4992	0.8198	0.036*
H9B	0.4210	0.4123	0.7441	0.036*
H9C	0.3491	0.4075	0.8487	0.036*
C10	0.7775 (2)	0.76175 (15)	0.83281 (14)	0.0234 (4)
C11	0.2749 (2)	0.68402 (15)	0.98983 (13)	0.0221 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0194 (2)	0.0187 (2)	0.0188 (2)	0.00166 (17)	−0.00064 (16)	0.00181 (17)
S2	0.0183 (2)	0.0185 (2)	0.0177 (2)	0.00097 (16)	−0.00023 (16)	0.00068 (17)
F1	0.0373 (7)	0.0179 (6)	0.0371 (7)	−0.0019 (5)	0.0017 (5)	0.0018 (5)
F2	0.0377 (6)	0.0311 (7)	0.0217 (6)	0.0021 (5)	0.0066 (5)	0.0019 (5)
F3	0.0198 (6)	0.0477 (9)	0.0490 (8)	−0.0072 (5)	−0.0028 (5)	0.0098 (7)
F4	0.0461 (7)	0.0298 (7)	0.0333 (7)	−0.0163 (6)	0.0131 (6)	−0.0077 (5)
F5	0.0296 (6)	0.0330 (7)	0.0306 (6)	0.0035 (5)	0.0110 (5)	−0.0009 (5)
F6	0.0389 (7)	0.0432 (8)	0.0219 (6)	0.0053 (6)	0.0003 (5)	0.0123 (5)
O1	0.0295 (7)	0.0210 (8)	0.0368 (8)	0.0062 (6)	0.0062 (6)	0.0035 (6)
O2	0.0270 (7)	0.0349 (9)	0.0192 (7)	0.0015 (6)	−0.0063 (5)	0.0005 (6)
O3	0.0225 (7)	0.0388 (9)	0.0217 (7)	0.0031 (6)	−0.0024 (5)	0.0091 (6)
O4	0.0260 (7)	0.0191 (7)	0.0349 (8)	−0.0001 (5)	0.0008 (6)	−0.0069 (6)
N1	0.0235 (7)	0.0208 (9)	0.0191 (7)	0.0020 (6)	0.0017 (6)	−0.0006 (6)
N2	0.0248 (8)	0.0203 (9)	0.0173 (7)	0.0009 (6)	0.0026 (6)	0.0001 (6)
N3	0.0191 (7)	0.0207 (9)	0.0189 (7)	−0.0003 (6)	−0.0011 (6)	−0.0047 (6)
C1	0.0241 (9)	0.0226 (10)	0.0177 (8)	−0.0064 (7)	−0.0024 (7)	−0.0027 (7)
C2	0.0194 (8)	0.0249 (10)	0.0214 (9)	−0.0030 (7)	0.0007 (7)	−0.0015 (8)
C3	0.0232 (8)	0.0146 (9)	0.0133 (8)	−0.0031 (7)	0.0015 (6)	0.0026 (6)
C4	0.0275 (9)	0.0180 (10)	0.0177 (8)	−0.0016 (7)	0.0038 (7)	0.0004 (7)
C5	0.0282 (10)	0.0263 (11)	0.0237 (9)	0.0080 (8)	−0.0012 (8)	0.0038 (8)
C6	0.0219 (9)	0.0259 (11)	0.0281 (10)	0.0074 (8)	−0.0027 (7)	−0.0009 (8)
C7	0.0272 (9)	0.0231 (11)	0.0225 (9)	−0.0008 (8)	0.0046 (7)	0.0051 (8)
C8	0.0258 (9)	0.0172 (9)	0.0138 (8)	0.0013 (7)	0.0009 (6)	−0.0014 (7)
C9	0.0218 (9)	0.0235 (10)	0.0260 (10)	0.0039 (7)	−0.0035 (7)	−0.0013 (8)
C10	0.0210 (9)	0.0241 (11)	0.0251 (9)	−0.0002 (7)	0.0001 (7)	0.0030 (8)
C11	0.0249 (9)	0.0234 (10)	0.0182 (9)	−0.0004 (7)	0.0020 (7)	−0.0006 (7)

Geometric parameters (Å, º) top

S1—O1	1.4273 (15)	C1—C2	1.384 (3)
S1—O2	1.4308 (14)	C1—C3ⁱ	1.387 (2)
S1—N3	1.5724 (15)	C1—H1	0.9500
S1—C10	1.836 (2)	C2—C3	1.390 (3)
S2—O4	1.4255 (14)	C2—H2	0.9500
S2—O3	1.4280 (14)	C3—C1ⁱ	1.387 (2)
S2—N3	1.5837 (16)	C3—C4	1.509 (2)
S2—C11	1.835 (2)	C4—H4A	0.9900
F1—C10	1.327 (2)	C4—H4B	0.9900
F2—C10	1.332 (2)	C5—C6	1.338 (3)
F3—C10	1.323 (2)	C5—H5	0.9500
F4—C11	1.331 (2)	C6—H6	0.9500
F5—C11	1.327 (2)	C7—H7A	0.9800
F6—C11	1.324 (2)	C7—H7B	0.9800
N1—C8	1.335 (2)	C7—H7C	0.9800
N1—C6	1.387 (2)	C8—C9	1.476 (3)
N1—C7	1.469 (2)	C9—H9A	0.9800
N2—C8	1.330 (2)	C9—H9B	0.9800
N2—C5	1.386 (2)	C9—H9C	0.9800
N2—C4	1.462 (2)

O1—S1—O2	118.48 (9)	C6—C5—N2	106.80 (17)
O1—S1—N3	108.59 (9)	C6—C5—H5	126.6
O2—S1—N3	116.33 (8)	N2—C5—H5	126.6
O1—S1—C10	103.95 (9)	C5—C6—N1	107.28 (17)
O2—S1—C10	105.12 (9)	C5—C6—H6	126.4
N3—S1—C10	102.19 (9)	N1—C6—H6	126.4
O4—S2—O3	119.43 (9)	N1—C7—H7A	109.5
O4—S2—N3	116.29 (8)	N1—C7—H7B	109.5
O3—S2—N3	107.98 (8)	H7A—C7—H7B	109.5
O4—S2—C11	104.56 (9)	N1—C7—H7C	109.5
O3—S2—C11	104.53 (9)	H7A—C7—H7C	109.5
N3—S2—C11	101.73 (9)	H7B—C7—H7C	109.5
C8—N1—C6	108.92 (16)	N2—C8—N1	107.58 (16)
C8—N1—C7	126.98 (16)	N2—C8—C9	125.43 (17)
C6—N1—C7	124.10 (16)	N1—C8—C9	126.99 (17)
C8—N2—C5	109.41 (16)	C8—C9—H9A	109.5
C8—N2—C4	125.98 (16)	C8—C9—H9B	109.5
C5—N2—C4	124.60 (16)	H9A—C9—H9B	109.5
S1—N3—S2	125.16 (10)	C8—C9—H9C	109.5
C2—C1—C3ⁱ	121.01 (17)	H9A—C9—H9C	109.5
C2—C1—H1	119.5	H9B—C9—H9C	109.5
C3ⁱ—C1—H1	119.5	F3—C10—F1	108.73 (17)
C1—C2—C3	119.81 (17)	F3—C10—F2	108.50 (16)
C1—C2—H2	120.1	F1—C10—F2	107.88 (16)
C3—C2—H2	120.1	F3—C10—S1	110.21 (13)
C1ⁱ—C3—C2	119.18 (17)	F1—C10—S1	111.04 (13)
C1ⁱ—C3—C4	119.47 (16)	F2—C10—S1	110.41 (14)
C2—C3—C4	121.31 (16)	F6—C11—F5	108.38 (15)
N2—C4—C3	112.97 (15)	F6—C11—F4	108.32 (17)
N2—C4—H4A	109.0	F5—C11—F4	107.65 (15)
C3—C4—H4A	109.0	F6—C11—S2	110.87 (13)
N2—C4—H4B	109.0	F5—C11—S2	110.29 (13)
C3—C4—H4B	109.0	F4—C11—S2	111.22 (12)
H4A—C4—H4B	107.8

O1—S1—N3—S2	159.88 (11)	C6—N1—C8—N2	0.8 (2)
O2—S1—N3—S2	23.18 (16)	C7—N1—C8—N2	−178.01 (17)
C10—S1—N3—S2	−90.68 (13)	C6—N1—C8—C9	−179.42 (18)
O4—S2—N3—S1	14.34 (16)	C7—N1—C8—C9	1.7 (3)
O3—S2—N3—S1	151.77 (12)	O1—S1—C10—F3	−67.76 (16)
C11—S2—N3—S1	−98.55 (13)	O2—S1—C10—F3	57.41 (16)
C3ⁱ—C1—C2—C3	0.3 (3)	N3—S1—C10—F3	179.31 (14)
C1—C2—C3—C1ⁱ	−0.3 (3)	O1—S1—C10—F1	171.70 (13)
C1—C2—C3—C4	177.36 (17)	O2—S1—C10—F1	−63.13 (15)
C8—N2—C4—C3	75.5 (2)	N3—S1—C10—F1	58.76 (15)
C5—N2—C4—C3	−104.1 (2)	O1—S1—C10—F2	52.09 (15)
C1ⁱ—C3—C4—N2	−140.06 (17)	O2—S1—C10—F2	177.26 (13)
C2—C3—C4—N2	42.3 (2)	N3—S1—C10—F2	−60.84 (15)
C8—N2—C5—C6	0.2 (2)	O4—S2—C11—F6	−59.50 (15)
C4—N2—C5—C6	179.92 (17)	O3—S2—C11—F6	174.21 (13)
N2—C5—C6—N1	0.3 (2)	N3—S2—C11—F6	61.92 (15)
C8—N1—C6—C5	−0.7 (2)	O4—S2—C11—F5	60.54 (15)
C7—N1—C6—C5	178.19 (18)	O3—S2—C11—F5	−65.75 (15)
C5—N2—C8—N1	−0.7 (2)	N3—S2—C11—F5	−178.04 (13)
C4—N2—C8—N1	179.66 (16)	O4—S2—C11—F4	179.90 (13)
C5—N2—C8—C9	179.58 (18)	O3—S2—C11—F4	53.62 (16)
C4—N2—C8—C9	−0.1 (3)	N3—S2—C11—F4	−58.68 (15)

Symmetry code: (i) −x+1, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	C₁₆H₂₄N₄²⁺·2C₂F₆NO₄S₂⁻
M_r	856.71
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	100
a, b, c (Å)	8.7195 (7), 13.710 (1), 13.8351 (11)
β (°)	92.290 (1)
V (Å³)	1652.6 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.41
Crystal size (mm)	0.40 × 0.30 × 0.20

Data collection
Diffractometer	Bruker SMART APEX diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.853, 0.922
No. of measured, independent and observed [I > 2σ(I)] reflections	10192, 3744, 3191
R_int	0.023
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.092, 1.02
No. of reflections	3744
No. of parameters	237
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.48, −0.41

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2010).

Acknowledgements

We thank the University of Malaya (grant No. TA010/2010 A) for supporting this study.

References

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