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organic compounds
Imidazolium-based ionic liquid salts: 3,3′-dimethyl-1,1′-(1,4-phenylenedimethylene)diimidazolium bis(tetrafluoroborate) and 3,3′-di-n-butyl-1,1′-(1,4-phenylenedimethylene)diimidazolium bis(trifluoromethanesulfonate)
aDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
*Correspondence e-mail: seikweng@um.edu.my
Crystallization of the ionic liquid 3,3′-dimethyl-1,1′-(1,4-phenylenedimethylene)diimidazolium bis(tetrafluoroborate), C16H20N42+·2BF4−, (I), from its solution in water has permitted the first single-crystal study of an imidazolium-based ionic liquid having a tetrafluoroborate ion as counter-ion. Despite the expectation that the anion would not participate in nonclassical hydrogen bonding, the ionic liquid features C—H⋯F hydrogen bonds. The dication lies about a center of inversion. The ionic liquid 3,3′-di-n-butyl-1,1′-(1,4-phenylenedimethylene)diimidazolium bis(trifluoromethanesulfonate), C22H32N42+·2CF3SO3−, (II), features both C—H⋯F and C—H⋯O hydrogen bonds.
Comment
Some ionic liquids incorporate an imidazolium group, as this feature appears to confer limited crystallinity despite the homogenous appearance of these ionic liquids. An understanding of the liquid–crystalline state of such compounds has been provided by the et al., 2003). A better understanding of the solid-state versus liquid-state structures is furnished by the of the hexafluorophosphate salt of 1-butyl-3-methylimidazolium (Dibrov & Kochi, 2006
). As the hexafluorophosphate anion does not normally participate in nonclassical hydrogen bonding, the probably better represents the inter-ionic interactions of the liquid–crystalline state.
Our interest in the 3,3′-dimethyl-1,1′-(1,4-phenylenedimethylene)diimidazolium dication arises from several reports on the applications of this class of ionic liquids. For example, 1-n-butyl-3-methylimidazolium tetrafluoroborate possesses an excellent gas-absorption property. As these studies have suggested that the nature of the anion influences this property (Aki et al., 2004; Anthony et al., 2005
; Galán Sánchez et al., 2007
), we synthesized several 3,3′-dimethyl-1,1′-(1,4-phenylenedimethylene)diimidazolium salts, viz. with the hexafluorophosphate, tetrafluoroborate and trifluoromethylsulfonate anions, and examined their 13C NMR properties in
![Ganesan, K. & Alias, Y. (2008). Int. J. Mol. Sci. 9, 1207-1213. [Ganesan, K. & Alias, Y. (2008). Int. J. Mol. Sci. 9, 1207-1213.]](../../../../../../logos/arrows/c_arr.gif)
![Holbrey, J. D. & Seddon, K. R. (1999). J. Chem. Soc. Dalton Trans. pp. 2133-2139. [Holbrey, J. D. & Seddon, K. R. (1999). J. Chem. Soc. Dalton Trans. pp. 2133-2139.]](../../../../../../logos/arrows/c_arr.gif)
3,3′-Dimethyl-1,1′-(1,4-phenylenedimethylene)diimidazolium bis(tetrafluoroborate), (I), exists as a dication and a monoanion (Fig. 1
) that interact weakly through C—H⋯F hydrogen bonding. The anion forms several contacts that are less than the sum of the van der Waals radii of hydrogen (1.2 Å) and fluorine (1.5 Å) (Table 1
). Two of the three hydrogen bonds, both from the imidazolium group, are significantly short (2.33 and 2.37 Å); moreover, these two hydrogen bonds are almost linear (171 and 162°, respectively). All distances between adjacent phenylene rings or between adjacent imidazolium rings exceed 4 Å. The bond dimensions of the dication are similar to those found in the hexachloroplatinate(IV) (Li & Liu, 2003
), tetrathiocyanatocadmate(II) (Liu et al., 2002
), tetraselenocyanocadmate (Liu & Li, 2003
) and tetrachloroargentate (Wang et al., 2005
) salts.
The bond dimensions of the tetrafluoroborate counter-anions are marginally different from those found in more flexible dications, viz. in 1,1′-methylenebis(3-methylimidazolium) dipicrate (Jin et al., 2006) and 3,3′-dimethyl-1,1′-ethylenediimidazolium dibromide (Jin et al., 2007
). The N—Cmethylene distance [1.470 (3) Å] is lengthened compared with those found in the dipicrate salt [1.457 (2) and 1.458 (2) Å] and the N—Cethylene distance found in the dibromide salt [1.461 (2) Å].
3,3′-Di-n-butyl-1,1′-(1,4-phenylenedimethylene)diimidazolium bis(trifluoromethanesulfonate), (II), also has the dication interacting with the monoanions (Fig. 2) through weak C—H⋯F hydrogen bonds. The imidazolium–phenylenedimethylene–imidazolium portion has a Z shape, with the butyl substituents at either end. One of the butyl groups has the usual zigzag shape, whereas the other has a U shape. The C—H⋯F interactions are somewhat longer and the hydrogen bonds more bent; however, two short linear C—H⋯O hydrogen bonds are present that are comparable with classical hydrogen bonds (Table 2
).
In the present study, because the two anions do not engage in strong hydrogen bonding, the ionic liquid state then probably requires cation–anion interactions for long-range crystallinity.
![]() | Figure 1 Displacement ellipsoid plot (Barbour, 2001 ![]() ![]() |
![]() | Figure 2 Displacement ellipsoid plot (Barbour, 2001 ![]() |
Experimental
The syntheses of the title compounds have been detailed in the study by Ganesan & Alias (2008). Crystals of both (I)
and (II) were grown from solutions in water.
Compound (I)![[link]](../../../../../../logos/arrows/c_arr.gif)
Crystal data
|
Data collection
|
Refinement
|
|
Compound (II)![[link]](../../../../../../logos/arrows/c_arr.gif)
Crystal data
|
Refinement
|
|
Carbon-bound H atoms were placed in calculated positions (C—H = 0.95–0.99 Å) and included in the Uiso(H) values set at 1.2–1.5Ueq(C).
in the riding model approximation, withFor both compounds, data collection: APEX2 (Bruker, 2007); cell SAINT (Bruker, 2007
); 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, 2008
).
Supporting information
10.1107/S0108270108023111/sk3257sup1.cif
contains datablocks I, II, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S0108270108023111/sk3257Isup2.hkl
Structure factors: contains datablock II. DOI: 10.1107/S0108270108023111/sk3257IIsup3.hkl
The synthesis of the title compounds have been detailed in the study by Ganesan & Alias (2008). Crystals of both (I) and (II) were grown from solutions in water.
Carbon-bound H atoms were placed in calculated positions (C—H = 0.95–0.99Å) and were included in the
in the riding model approximation, with Uiso(H) values set at 1.2–1.5Ueq(C).For both compounds, data collection: APEX2 (Bruker, 2007); cell
SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); 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, 2008).C16H20N42+·2BF4− | F(000) = 452 |
Mr = 441.98 | Dx = 1.509 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 1143 reflections |
a = 4.9517 (2) Å | θ = 3.1–21.1° |
b = 12.8674 (5) Å | µ = 0.14 mm−1 |
c = 15.2828 (6) Å | T = 100 K |
β = 92.806 (3)° | Prism, colorless |
V = 972.58 (7) Å3 | 0.36 × 0.08 × 0.06 mm |
Z = 2 |
Bruker SMART APEX diffractometer | 1364 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.075 |
Graphite monochromator | θmax = 27.5°, θmin = 2.1° |
ω scans | h = −4→6 |
8044 measured reflections | k = −16→16 |
2231 independent reflections | l = −19→19 |
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)] = 0.050 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.120 | H-atom parameters constrained |
S = 1.02 | w = 1/[σ2(Fo2) + (0.0322P)2 + 0.1741P] where P = (Fo2 + 2Fc2)/3 |
2231 reflections | (Δ/σ)max = 0.001 |
137 parameters | Δρmax = 0.24 e Å−3 |
0 restraints | Δρmin = −0.30 e Å−3 |
C16H20N42+·2BF4− | V = 972.58 (7) Å3 |
Mr = 441.98 | Z = 2 |
Monoclinic, P21/c | Mo Kα radiation |
a = 4.9517 (2) Å | µ = 0.14 mm−1 |
b = 12.8674 (5) Å | T = 100 K |
c = 15.2828 (6) Å | 0.36 × 0.08 × 0.06 mm |
β = 92.806 (3)° |
Bruker SMART APEX diffractometer | 1364 reflections with I > 2σ(I) |
8044 measured reflections | Rint = 0.075 |
2231 independent reflections |
R[F2 > 2σ(F2)] = 0.050 | 0 restraints |
wR(F2) = 0.120 | H-atom parameters constrained |
S = 1.02 | Δρmax = 0.24 e Å−3 |
2231 reflections | Δρmin = −0.30 e Å−3 |
137 parameters |
x | y | z | Uiso*/Ueq | ||
F1 | −0.0369 (3) | −0.09457 (12) | 0.37770 (8) | 0.0479 (4) | |
F2 | −0.3740 (3) | −0.18188 (11) | 0.30416 (8) | 0.0428 (4) | |
F3 | 0.0400 (3) | −0.25596 (11) | 0.32458 (9) | 0.0465 (4) | |
F4 | −0.0191 (3) | −0.12118 (10) | 0.23071 (8) | 0.0385 (4) | |
B1 | −0.0979 (5) | −0.16353 (19) | 0.30921 (15) | 0.0249 (6) | |
N1 | 0.4613 (4) | 0.12459 (13) | 0.35072 (11) | 0.0290 (5) | |
N2 | 0.6742 (4) | 0.23055 (13) | 0.43856 (11) | 0.0247 (4) | |
C1 | 0.3753 (6) | 0.06816 (18) | 0.27075 (15) | 0.0440 (7) | |
H1A | 0.4430 | 0.1041 | 0.2197 | 0.066* | |
H1B | 0.1774 | 0.0653 | 0.2656 | 0.066* | |
H1C | 0.4482 | −0.0026 | 0.2735 | 0.066* | |
C2 | 0.3762 (5) | 0.10498 (17) | 0.43359 (14) | 0.0325 (6) | |
H2 | 0.2484 | 0.0540 | 0.4491 | 0.039* | |
C3 | 0.5081 (5) | 0.17169 (16) | 0.48851 (14) | 0.0305 (5) | |
H3 | 0.4900 | 0.1771 | 0.5499 | 0.037* | |
C4 | 0.6401 (5) | 0.20069 (16) | 0.35528 (14) | 0.0272 (5) | |
H4 | 0.7296 | 0.2294 | 0.3073 | 0.033* | |
C5 | 0.8375 (5) | 0.31988 (16) | 0.46940 (14) | 0.0285 (5) | |
H5A | 0.9690 | 0.3379 | 0.4250 | 0.034* | |
H5B | 0.9403 | 0.3011 | 0.5243 | 0.034* | |
C6 | 0.6599 (5) | 0.41291 (16) | 0.48553 (13) | 0.0237 (5) | |
C7 | 0.4668 (5) | 0.44517 (16) | 0.42275 (13) | 0.0284 (5) | |
H7 | 0.4441 | 0.4079 | 0.3692 | 0.034* | |
C8 | 0.3062 (5) | 0.53107 (16) | 0.43693 (13) | 0.0280 (5) | |
H8 | 0.1728 | 0.5517 | 0.3936 | 0.034* |
U11 | U22 | U33 | U12 | U13 | U23 | |
F1 | 0.0565 (11) | 0.0587 (9) | 0.0288 (7) | −0.0192 (8) | 0.0049 (7) | −0.0132 (6) |
F2 | 0.0309 (8) | 0.0568 (10) | 0.0407 (8) | −0.0030 (7) | 0.0027 (6) | −0.0077 (6) |
F3 | 0.0471 (10) | 0.0460 (9) | 0.0465 (9) | 0.0092 (7) | 0.0026 (7) | 0.0130 (6) |
F4 | 0.0456 (10) | 0.0459 (9) | 0.0241 (7) | −0.0010 (7) | 0.0022 (6) | 0.0057 (5) |
B1 | 0.0257 (15) | 0.0292 (13) | 0.0199 (12) | −0.0030 (11) | 0.0028 (11) | 0.0017 (10) |
N1 | 0.0373 (12) | 0.0221 (9) | 0.0275 (10) | −0.0010 (8) | −0.0002 (9) | −0.0018 (7) |
N2 | 0.0308 (11) | 0.0208 (9) | 0.0228 (9) | −0.0004 (8) | 0.0027 (8) | 0.0015 (7) |
C1 | 0.0584 (19) | 0.0326 (13) | 0.0396 (14) | −0.0025 (13) | −0.0102 (13) | −0.0096 (11) |
C2 | 0.0372 (15) | 0.0257 (12) | 0.0352 (13) | −0.0006 (11) | 0.0063 (11) | 0.0089 (9) |
C3 | 0.0387 (14) | 0.0266 (12) | 0.0269 (11) | 0.0027 (11) | 0.0064 (10) | 0.0053 (9) |
C4 | 0.0318 (14) | 0.0251 (11) | 0.0252 (11) | 0.0011 (10) | 0.0059 (10) | 0.0009 (9) |
C5 | 0.0295 (13) | 0.0283 (12) | 0.0275 (11) | −0.0035 (10) | −0.0025 (10) | −0.0007 (9) |
C6 | 0.0258 (12) | 0.0222 (11) | 0.0233 (10) | −0.0047 (9) | 0.0019 (9) | 0.0029 (8) |
C7 | 0.0366 (14) | 0.0280 (12) | 0.0200 (10) | −0.0004 (10) | −0.0038 (10) | −0.0034 (8) |
C8 | 0.0307 (13) | 0.0288 (12) | 0.0238 (11) | 0.0006 (10) | −0.0063 (10) | 0.0015 (9) |
F1—B1 | 1.394 (3) | C2—C3 | 1.347 (3) |
F2—B1 | 1.386 (3) | C2—H2 | 0.9500 |
F3—B1 | 1.386 (3) | C3—H3 | 0.9500 |
F4—B1 | 1.391 (3) | C4—H4 | 0.9500 |
N1—C4 | 1.320 (3) | C5—C6 | 1.513 (3) |
N1—C2 | 1.378 (3) | C5—H5A | 0.9900 |
N1—C1 | 1.467 (3) | C5—H5B | 0.9900 |
N2—C4 | 1.332 (3) | C6—C7 | 1.385 (3) |
N2—C3 | 1.376 (3) | C6—C8i | 1.390 (3) |
N2—C5 | 1.470 (3) | C7—C8 | 1.385 (3) |
C1—H1A | 0.9800 | C7—H7 | 0.9500 |
C1—H1B | 0.9800 | C8—C6i | 1.390 (3) |
C1—H1C | 0.9800 | C8—H8 | 0.9500 |
F2—B1—F3 | 109.86 (19) | C2—C3—N2 | 106.84 (19) |
F2—B1—F4 | 109.65 (18) | C2—C3—H3 | 126.6 |
F3—B1—F4 | 109.02 (18) | N2—C3—H3 | 126.6 |
F2—B1—F1 | 109.10 (19) | N1—C4—N2 | 108.52 (19) |
F3—B1—F1 | 109.40 (18) | N1—C4—H4 | 125.7 |
F4—B1—F1 | 109.80 (19) | N2—C4—H4 | 125.7 |
C4—N1—C2 | 108.78 (18) | N2—C5—C6 | 110.85 (19) |
C4—N1—C1 | 125.3 (2) | N2—C5—H5A | 109.5 |
C2—N1—C1 | 125.9 (2) | C6—C5—H5A | 109.5 |
C4—N2—C3 | 108.68 (19) | N2—C5—H5B | 109.5 |
C4—N2—C5 | 125.01 (18) | C6—C5—H5B | 109.5 |
C3—N2—C5 | 125.93 (17) | H5A—C5—H5B | 108.1 |
N1—C1—H1A | 109.5 | C7—C6—C8i | 119.0 (2) |
N1—C1—H1B | 109.5 | C7—C6—C5 | 120.77 (18) |
H1A—C1—H1B | 109.5 | C8i—C6—C5 | 120.16 (18) |
N1—C1—H1C | 109.5 | C8—C7—C6 | 120.87 (18) |
H1A—C1—H1C | 109.5 | C8—C7—H7 | 119.6 |
H1B—C1—H1C | 109.5 | C6—C7—H7 | 119.6 |
C3—C2—N1 | 107.2 (2) | C7—C8—C6i | 120.1 (2) |
C3—C2—H2 | 126.4 | C7—C8—H8 | 120.0 |
N1—C2—H2 | 126.4 | C6i—C8—H8 | 120.0 |
C4—N1—C2—C3 | 0.2 (3) | C5—N2—C4—N1 | −173.92 (19) |
C1—N1—C2—C3 | 178.3 (2) | C4—N2—C5—C6 | 100.0 (2) |
N1—C2—C3—N2 | −0.6 (3) | C3—N2—C5—C6 | −72.2 (3) |
C4—N2—C3—C2 | 0.8 (3) | N2—C5—C6—C7 | −49.6 (3) |
C5—N2—C3—C2 | 174.0 (2) | N2—C5—C6—C8i | 132.1 (2) |
C2—N1—C4—N2 | 0.3 (3) | C8i—C6—C7—C8 | −0.9 (3) |
C1—N1—C4—N2 | −177.8 (2) | C5—C6—C7—C8 | −179.2 (2) |
C3—N2—C4—N1 | −0.6 (3) | C6—C7—C8—C6i | 0.9 (4) |
Symmetry code: (i) −x+1, −y+1, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2···F1 | 0.95 | 2.59 | 3.367 (3) | 140 |
C3—H3···F2ii | 0.95 | 2.33 | 3.272 (3) | 171 |
C4—H4···F3iii | 0.95 | 2.37 | 3.287 (3) | 162 |
C4—H4···F4iii | 0.95 | 2.48 | 3.278 (3) | 141 |
Symmetry codes: (ii) −x, −y, −z+1; (iii) −x+1, y+1/2, −z+1/2. |
C22H32N42+·2CF3O3S− | Z = 2 |
Mr = 650.66 | F(000) = 676 |
Triclinic, P1 | Dx = 1.487 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 10.3833 (1) Å | Cell parameters from 9889 reflections |
b = 12.0470 (2) Å | θ = 2.3–28.3° |
c = 13.6933 (2) Å | µ = 0.27 mm−1 |
α = 100.752 (1)° | T = 100 K |
β = 105.194 (1)° | Prism, colorless |
γ = 111.970 (1)° | 0.44 × 0.22 × 0.07 mm |
V = 1453.36 (4) Å3 |
Bruker SMART APEX diffractometer | 6636 independent reflections |
Radiation source: fine-focus sealed tube | 5673 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.035 |
ω scans | θmax = 27.5°, θmin = 2.2° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −13→13 |
Tmin = 0.878, Tmax = 0.982 | k = −15→15 |
18621 measured reflections | l = −17→17 |
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)] = 0.035 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.101 | H-atom parameters constrained |
S = 1.02 | w = 1/[σ2(Fo2) + (0.0519P)2 + 0.5009P] where P = (Fo2 + 2Fc2)/3 |
6636 reflections | (Δ/σ)max = 0.001 |
379 parameters | Δρmax = 0.61 e Å−3 |
0 restraints | Δρmin = −0.53 e Å−3 |
C22H32N42+·2CF3O3S− | γ = 111.970 (1)° |
Mr = 650.66 | V = 1453.36 (4) Å3 |
Triclinic, P1 | Z = 2 |
a = 10.3833 (1) Å | Mo Kα radiation |
b = 12.0470 (2) Å | µ = 0.27 mm−1 |
c = 13.6933 (2) Å | T = 100 K |
α = 100.752 (1)° | 0.44 × 0.22 × 0.07 mm |
β = 105.194 (1)° |
Bruker SMART APEX diffractometer | 6636 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 5673 reflections with I > 2σ(I) |
Tmin = 0.878, Tmax = 0.982 | Rint = 0.035 |
18621 measured reflections |
R[F2 > 2σ(F2)] = 0.035 | 0 restraints |
wR(F2) = 0.101 | H-atom parameters constrained |
S = 1.02 | Δρmax = 0.61 e Å−3 |
6636 reflections | Δρmin = −0.53 e Å−3 |
379 parameters |
x | y | z | Uiso*/Ueq | ||
S1 | 0.35898 (4) | 0.60056 (3) | 0.40873 (3) | 0.02218 (9) | |
S2 | 0.19275 (4) | 0.80463 (3) | 0.89593 (3) | 0.02267 (10) | |
O4 | 0.20342 (16) | 0.70622 (12) | 0.82642 (11) | 0.0471 (4) | |
O5 | 0.30956 (14) | 0.92924 (11) | 0.92008 (9) | 0.0351 (3) | |
O6 | 0.04659 (14) | 0.79708 (15) | 0.87344 (11) | 0.0451 (3) | |
F1 | 0.12047 (11) | 0.52767 (13) | 0.24022 (9) | 0.0540 (3) | |
F2 | 0.24536 (16) | 0.72806 (14) | 0.31126 (12) | 0.0657 (4) | |
F3 | 0.32545 (13) | 0.62352 (17) | 0.21915 (9) | 0.0669 (4) | |
F4 | 0.13506 (13) | 0.65721 (10) | 1.01335 (9) | 0.0435 (3) | |
F5 | 0.21473 (17) | 0.85268 (12) | 1.09557 (9) | 0.0622 (4) | |
F6 | 0.36549 (15) | 0.7829 (2) | 1.06021 (15) | 0.0957 (7) | |
O1 | 0.50364 (12) | 0.70784 (11) | 0.44797 (9) | 0.0307 (2) | |
O2 | 0.27230 (13) | 0.60151 (12) | 0.47503 (9) | 0.0338 (3) | |
O3 | 0.35967 (15) | 0.48197 (12) | 0.36869 (11) | 0.0442 (3) | |
N1 | 0.12621 (14) | 0.33416 (12) | 0.51096 (10) | 0.0230 (3) | |
N2 | 0.25131 (13) | 0.45401 (11) | 0.67469 (10) | 0.0216 (2) | |
N3 | 0.28240 (13) | 0.17453 (11) | 1.10979 (9) | 0.0202 (2) | |
N4 | 0.46277 (13) | 0.18255 (11) | 1.23701 (9) | 0.0198 (2) | |
C1 | 0.0529 (2) | −0.09095 (18) | 0.31598 (15) | 0.0428 (4) | |
H1A | 0.0180 | −0.1515 | 0.2450 | 0.064* | |
H1B | −0.0100 | −0.1277 | 0.3549 | 0.064* | |
H1C | 0.1564 | −0.0712 | 0.3554 | 0.064* | |
C2 | 0.04383 (18) | 0.02908 (15) | 0.30444 (12) | 0.0281 (3) | |
H2A | −0.0604 | 0.0083 | 0.2627 | 0.034* | |
H2B | 0.1067 | 0.0654 | 0.2645 | 0.034* | |
C3 | 0.09533 (18) | 0.12680 (15) | 0.41241 (12) | 0.0277 (3) | |
H3A | 0.0335 | 0.0893 | 0.4526 | 0.033* | |
H3B | 0.1999 | 0.1477 | 0.4534 | 0.033* | |
C4 | 0.0859 (2) | 0.24743 (15) | 0.40443 (12) | 0.0306 (3) | |
H4A | 0.1542 | 0.2895 | 0.3699 | 0.037* | |
H4B | −0.0168 | 0.2269 | 0.3594 | 0.037* | |
C5 | 0.03659 (17) | 0.38007 (15) | 0.54414 (13) | 0.0264 (3) | |
H5 | −0.0619 | 0.3625 | 0.5026 | 0.032* | |
C6 | 0.11439 (17) | 0.45476 (15) | 0.64665 (13) | 0.0261 (3) | |
H6 | 0.0810 | 0.4993 | 0.6909 | 0.031* | |
C7 | 0.25546 (16) | 0.38050 (14) | 0.59125 (12) | 0.0227 (3) | |
H7 | 0.3375 | 0.3639 | 0.5895 | 0.027* | |
C8 | 0.36507 (17) | 0.50969 (14) | 0.78388 (12) | 0.0270 (3) | |
H8A | 0.3712 | 0.5922 | 0.8188 | 0.032* | |
H8B | 0.4638 | 0.5241 | 0.7803 | 0.032* | |
C9 | 0.32536 (16) | 0.42248 (14) | 0.84876 (11) | 0.0228 (3) | |
C10 | 0.37125 (17) | 0.32777 (15) | 0.84560 (12) | 0.0266 (3) | |
H10 | 0.4352 | 0.3234 | 0.8081 | 0.032* | |
C11 | 0.32457 (17) | 0.23983 (15) | 0.89656 (12) | 0.0254 (3) | |
H11 | 0.3558 | 0.1749 | 0.8932 | 0.031* | |
C12 | 0.23232 (15) | 0.24606 (14) | 0.95255 (10) | 0.0204 (3) | |
C13 | 0.19133 (18) | 0.34377 (16) | 0.95932 (12) | 0.0281 (3) | |
H13 | 0.1314 | 0.3507 | 0.9997 | 0.034* | |
C14 | 0.23738 (19) | 0.43124 (15) | 0.90740 (13) | 0.0302 (3) | |
H14 | 0.2084 | 0.4975 | 0.9121 | 0.036* | |
C15 | 0.17564 (16) | 0.14543 (14) | 1.00239 (11) | 0.0234 (3) | |
H15A | 0.0794 | 0.1377 | 1.0075 | 0.028* | |
H15B | 0.1577 | 0.0634 | 0.9561 | 0.028* | |
C16 | 0.38742 (16) | 0.13506 (13) | 1.13235 (11) | 0.0217 (3) | |
H16 | 0.4053 | 0.0822 | 1.0823 | 0.026* | |
C17 | 0.40518 (16) | 0.25546 (14) | 1.28251 (11) | 0.0221 (3) | |
H17 | 0.4383 | 0.3002 | 1.3562 | 0.026* | |
C18 | 0.29276 (16) | 0.25131 (14) | 1.20272 (11) | 0.0217 (3) | |
H18 | 0.2325 | 0.2932 | 1.2094 | 0.026* | |
C19 | 0.57912 (16) | 0.15253 (15) | 1.29570 (11) | 0.0236 (3) | |
H19A | 0.6671 | 0.2317 | 1.3444 | 0.028* | |
H19B | 0.6106 | 0.1092 | 1.2446 | 0.028* | |
C20 | 0.52204 (18) | 0.06855 (15) | 1.35970 (12) | 0.0255 (3) | |
H20A | 0.4320 | −0.0092 | 1.3111 | 0.031* | |
H20B | 0.4934 | 0.1131 | 1.4121 | 0.031* | |
C21 | 0.63929 (19) | 0.03276 (17) | 1.41846 (13) | 0.0312 (3) | |
H21A | 0.7323 | 0.1106 | 1.4621 | 0.037* | |
H21B | 0.6037 | −0.0108 | 1.4675 | 0.037* | |
C22 | 0.6731 (2) | −0.05213 (19) | 1.34335 (16) | 0.0391 (4) | |
H22A | 0.7490 | −0.0721 | 1.3848 | 0.059* | |
H22B | 0.7101 | −0.0089 | 1.2954 | 0.059* | |
H22C | 0.5819 | −0.1304 | 1.3012 | 0.059* | |
C23 | 0.25700 (18) | 0.62153 (19) | 0.28899 (14) | 0.0356 (4) | |
C24 | 0.22960 (19) | 0.77210 (18) | 1.02249 (14) | 0.0355 (4) |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.02255 (18) | 0.02017 (18) | 0.02409 (17) | 0.01139 (14) | 0.00857 (13) | 0.00360 (13) |
S2 | 0.02470 (18) | 0.02235 (19) | 0.02051 (17) | 0.01095 (15) | 0.00926 (13) | 0.00338 (13) |
O4 | 0.0627 (9) | 0.0263 (7) | 0.0530 (8) | 0.0135 (6) | 0.0400 (7) | 0.0005 (6) |
O5 | 0.0468 (7) | 0.0236 (6) | 0.0294 (6) | 0.0086 (5) | 0.0187 (5) | 0.0048 (5) |
O6 | 0.0339 (7) | 0.0700 (10) | 0.0448 (7) | 0.0321 (7) | 0.0145 (6) | 0.0283 (7) |
F1 | 0.0225 (5) | 0.0804 (9) | 0.0379 (6) | 0.0105 (5) | 0.0040 (4) | 0.0097 (6) |
F2 | 0.0703 (9) | 0.0662 (9) | 0.0821 (10) | 0.0468 (8) | 0.0210 (7) | 0.0447 (8) |
F3 | 0.0375 (6) | 0.1312 (13) | 0.0353 (6) | 0.0310 (8) | 0.0212 (5) | 0.0363 (7) |
F4 | 0.0540 (7) | 0.0349 (6) | 0.0590 (7) | 0.0239 (5) | 0.0321 (6) | 0.0271 (5) |
F5 | 0.0985 (10) | 0.0415 (7) | 0.0259 (5) | 0.0098 (7) | 0.0265 (6) | 0.0062 (5) |
F6 | 0.0346 (7) | 0.1609 (18) | 0.1122 (13) | 0.0419 (9) | 0.0186 (7) | 0.1031 (13) |
O1 | 0.0229 (5) | 0.0292 (6) | 0.0323 (6) | 0.0094 (5) | 0.0072 (4) | 0.0022 (5) |
O2 | 0.0354 (6) | 0.0398 (7) | 0.0327 (6) | 0.0173 (6) | 0.0195 (5) | 0.0138 (5) |
O3 | 0.0448 (7) | 0.0269 (6) | 0.0566 (8) | 0.0221 (6) | 0.0125 (6) | −0.0001 (6) |
N1 | 0.0278 (6) | 0.0220 (6) | 0.0246 (6) | 0.0128 (5) | 0.0127 (5) | 0.0109 (5) |
N2 | 0.0240 (6) | 0.0198 (6) | 0.0242 (6) | 0.0101 (5) | 0.0114 (5) | 0.0095 (5) |
N3 | 0.0241 (6) | 0.0183 (6) | 0.0179 (5) | 0.0083 (5) | 0.0084 (5) | 0.0062 (4) |
N4 | 0.0239 (6) | 0.0190 (6) | 0.0191 (5) | 0.0102 (5) | 0.0098 (5) | 0.0075 (4) |
C1 | 0.0492 (11) | 0.0344 (10) | 0.0332 (9) | 0.0233 (9) | −0.0015 (8) | −0.0004 (7) |
C2 | 0.0284 (7) | 0.0262 (8) | 0.0254 (7) | 0.0089 (6) | 0.0097 (6) | 0.0056 (6) |
C3 | 0.0297 (8) | 0.0242 (8) | 0.0238 (7) | 0.0103 (6) | 0.0058 (6) | 0.0055 (6) |
C4 | 0.0434 (9) | 0.0280 (8) | 0.0224 (7) | 0.0161 (7) | 0.0136 (7) | 0.0098 (6) |
C5 | 0.0255 (7) | 0.0263 (8) | 0.0347 (8) | 0.0147 (6) | 0.0138 (6) | 0.0145 (6) |
C6 | 0.0293 (7) | 0.0251 (8) | 0.0337 (8) | 0.0164 (6) | 0.0177 (6) | 0.0128 (6) |
C7 | 0.0249 (7) | 0.0243 (7) | 0.0272 (7) | 0.0139 (6) | 0.0145 (6) | 0.0126 (6) |
C8 | 0.0288 (7) | 0.0200 (7) | 0.0258 (7) | 0.0061 (6) | 0.0075 (6) | 0.0070 (6) |
C9 | 0.0240 (7) | 0.0182 (7) | 0.0211 (6) | 0.0066 (6) | 0.0059 (5) | 0.0050 (5) |
C10 | 0.0252 (7) | 0.0310 (8) | 0.0323 (8) | 0.0160 (6) | 0.0163 (6) | 0.0137 (6) |
C11 | 0.0274 (7) | 0.0273 (8) | 0.0300 (7) | 0.0177 (6) | 0.0130 (6) | 0.0119 (6) |
C12 | 0.0206 (6) | 0.0209 (7) | 0.0164 (6) | 0.0081 (6) | 0.0041 (5) | 0.0047 (5) |
C13 | 0.0369 (8) | 0.0315 (8) | 0.0280 (7) | 0.0217 (7) | 0.0192 (6) | 0.0114 (6) |
C14 | 0.0448 (9) | 0.0265 (8) | 0.0318 (8) | 0.0236 (7) | 0.0199 (7) | 0.0113 (6) |
C15 | 0.0236 (7) | 0.0228 (7) | 0.0193 (6) | 0.0078 (6) | 0.0050 (5) | 0.0065 (5) |
C16 | 0.0290 (7) | 0.0190 (7) | 0.0197 (6) | 0.0116 (6) | 0.0112 (5) | 0.0070 (5) |
C17 | 0.0257 (7) | 0.0221 (7) | 0.0207 (6) | 0.0107 (6) | 0.0119 (5) | 0.0066 (5) |
C18 | 0.0246 (7) | 0.0206 (7) | 0.0211 (6) | 0.0097 (6) | 0.0110 (5) | 0.0057 (5) |
C19 | 0.0265 (7) | 0.0259 (7) | 0.0238 (7) | 0.0147 (6) | 0.0106 (6) | 0.0113 (6) |
C20 | 0.0338 (8) | 0.0280 (8) | 0.0258 (7) | 0.0184 (7) | 0.0173 (6) | 0.0134 (6) |
C21 | 0.0386 (9) | 0.0349 (9) | 0.0277 (7) | 0.0205 (7) | 0.0124 (7) | 0.0175 (7) |
C22 | 0.0436 (10) | 0.0466 (11) | 0.0519 (11) | 0.0332 (9) | 0.0270 (9) | 0.0279 (9) |
C23 | 0.0241 (7) | 0.0534 (11) | 0.0317 (8) | 0.0166 (8) | 0.0123 (6) | 0.0172 (8) |
C24 | 0.0291 (8) | 0.0407 (10) | 0.0351 (8) | 0.0136 (7) | 0.0077 (7) | 0.0184 (8) |
S1—O3 | 1.4350 (12) | C4—H4B | 0.9900 |
S1—O2 | 1.4376 (11) | C5—C6 | 1.350 (2) |
S1—O1 | 1.4424 (12) | C5—H5 | 0.9500 |
S1—C23 | 1.8216 (17) | C6—H6 | 0.9500 |
S2—O6 | 1.4310 (12) | C7—H7 | 0.9500 |
S2—O4 | 1.4340 (12) | C8—C9 | 1.510 (2) |
S2—O5 | 1.4408 (12) | C8—H8A | 0.9900 |
S2—C24 | 1.8226 (17) | C8—H8B | 0.9900 |
F1—C23 | 1.325 (2) | C9—C14 | 1.384 (2) |
F2—C23 | 1.321 (2) | C9—C10 | 1.389 (2) |
F3—C23 | 1.3314 (19) | C10—C11 | 1.383 (2) |
F4—C24 | 1.323 (2) | C10—H10 | 0.9500 |
F5—C24 | 1.341 (2) | C11—C12 | 1.3886 (19) |
F6—C24 | 1.315 (2) | C11—H11 | 0.9500 |
N1—C7 | 1.3260 (19) | C12—C13 | 1.389 (2) |
N1—C5 | 1.3752 (19) | C12—C15 | 1.506 (2) |
N1—C4 | 1.4761 (19) | C13—C14 | 1.388 (2) |
N2—C7 | 1.3299 (18) | C13—H13 | 0.9500 |
N2—C6 | 1.3760 (19) | C14—H14 | 0.9500 |
N2—C8 | 1.4791 (19) | C15—H15A | 0.9900 |
N3—C16 | 1.3330 (18) | C15—H15B | 0.9900 |
N3—C18 | 1.3788 (17) | C16—H16 | 0.9500 |
N3—C15 | 1.4754 (17) | C17—C18 | 1.351 (2) |
N4—C16 | 1.3284 (18) | C17—H17 | 0.9500 |
N4—C17 | 1.3788 (18) | C18—H18 | 0.9500 |
N4—C19 | 1.4707 (18) | C19—C20 | 1.516 (2) |
C1—C2 | 1.518 (2) | C19—H19A | 0.9900 |
C1—H1A | 0.9800 | C19—H19B | 0.9900 |
C1—H1B | 0.9800 | C20—C21 | 1.524 (2) |
C1—H1C | 0.9800 | C20—H20A | 0.9900 |
C2—C3 | 1.524 (2) | C20—H20B | 0.9900 |
C2—H2A | 0.9900 | C21—C22 | 1.514 (2) |
C2—H2B | 0.9900 | C21—H21A | 0.9900 |
C3—C4 | 1.514 (2) | C21—H21B | 0.9900 |
C3—H3A | 0.9900 | C22—H22A | 0.9800 |
C3—H3B | 0.9900 | C22—H22B | 0.9800 |
C4—H4A | 0.9900 | C22—H22C | 0.9800 |
O3—S1—O2 | 115.55 (8) | C11—C10—C9 | 120.56 (13) |
O3—S1—O1 | 113.96 (7) | C11—C10—H10 | 119.7 |
O2—S1—O1 | 114.84 (7) | C9—C10—H10 | 119.7 |
O3—S1—C23 | 103.19 (9) | C10—C11—C12 | 120.26 (13) |
O2—S1—C23 | 103.63 (7) | C10—C11—H11 | 119.9 |
O1—S1—C23 | 103.44 (8) | C12—C11—H11 | 119.9 |
O6—S2—O4 | 115.72 (9) | C11—C12—C13 | 119.17 (14) |
O6—S2—O5 | 114.78 (9) | C11—C12—C15 | 119.56 (13) |
O4—S2—O5 | 114.35 (7) | C13—C12—C15 | 121.26 (13) |
O6—S2—C24 | 102.42 (8) | C14—C13—C12 | 120.39 (13) |
O4—S2—C24 | 103.22 (9) | C14—C13—H13 | 119.8 |
O5—S2—C24 | 103.96 (8) | C12—C13—H13 | 119.8 |
C7—N1—C5 | 108.42 (13) | C9—C14—C13 | 120.34 (14) |
C7—N1—C4 | 125.51 (13) | C9—C14—H14 | 119.8 |
C5—N1—C4 | 126.07 (13) | C13—C14—H14 | 119.8 |
C7—N2—C6 | 108.63 (12) | N3—C15—C12 | 111.74 (12) |
C7—N2—C8 | 125.57 (12) | N3—C15—H15A | 109.3 |
C6—N2—C8 | 125.19 (12) | C12—C15—H15A | 109.3 |
C16—N3—C18 | 109.07 (12) | N3—C15—H15B | 109.3 |
C16—N3—C15 | 125.81 (12) | C12—C15—H15B | 109.3 |
C18—N3—C15 | 125.08 (12) | H15A—C15—H15B | 107.9 |
C16—N4—C17 | 108.93 (12) | N4—C16—N3 | 108.12 (12) |
C16—N4—C19 | 125.32 (12) | N4—C16—H16 | 125.9 |
C17—N4—C19 | 125.52 (12) | N3—C16—H16 | 125.9 |
C2—C1—H1A | 109.5 | C18—C17—N4 | 107.16 (12) |
C2—C1—H1B | 109.5 | C18—C17—H17 | 126.4 |
H1A—C1—H1B | 109.5 | N4—C17—H17 | 126.4 |
C2—C1—H1C | 109.5 | C17—C18—N3 | 106.71 (12) |
H1A—C1—H1C | 109.5 | C17—C18—H18 | 126.6 |
H1B—C1—H1C | 109.5 | N3—C18—H18 | 126.6 |
C1—C2—C3 | 111.95 (13) | N4—C19—C20 | 110.74 (12) |
C1—C2—H2A | 109.2 | N4—C19—H19A | 109.5 |
C3—C2—H2A | 109.2 | C20—C19—H19A | 109.5 |
C1—C2—H2B | 109.2 | N4—C19—H19B | 109.5 |
C3—C2—H2B | 109.2 | C20—C19—H19B | 109.5 |
H2A—C2—H2B | 107.9 | H19A—C19—H19B | 108.1 |
C4—C3—C2 | 113.64 (13) | C19—C20—C21 | 111.66 (13) |
C4—C3—H3A | 108.8 | C19—C20—H20A | 109.3 |
C2—C3—H3A | 108.8 | C21—C20—H20A | 109.3 |
C4—C3—H3B | 108.8 | C19—C20—H20B | 109.3 |
C2—C3—H3B | 108.8 | C21—C20—H20B | 109.3 |
H3A—C3—H3B | 107.7 | H20A—C20—H20B | 108.0 |
N1—C4—C3 | 111.08 (12) | C22—C21—C20 | 112.62 (13) |
N1—C4—H4A | 109.4 | C22—C21—H21A | 109.1 |
C3—C4—H4A | 109.4 | C20—C21—H21A | 109.1 |
N1—C4—H4B | 109.4 | C22—C21—H21B | 109.1 |
C3—C4—H4B | 109.4 | C20—C21—H21B | 109.1 |
H4A—C4—H4B | 108.0 | H21A—C21—H21B | 107.8 |
C6—C5—N1 | 107.39 (13) | C21—C22—H22A | 109.5 |
C6—C5—H5 | 126.3 | C21—C22—H22B | 109.5 |
N1—C5—H5 | 126.3 | H22A—C22—H22B | 109.5 |
C5—C6—N2 | 106.80 (13) | C21—C22—H22C | 109.5 |
C5—C6—H6 | 126.6 | H22A—C22—H22C | 109.5 |
N2—C6—H6 | 126.6 | H22B—C22—H22C | 109.5 |
N1—C7—N2 | 108.76 (12) | F2—C23—F1 | 107.89 (15) |
N1—C7—H7 | 125.6 | F2—C23—F3 | 108.10 (17) |
N2—C7—H7 | 125.6 | F1—C23—F3 | 106.88 (15) |
N2—C8—C9 | 110.24 (12) | F2—C23—S1 | 111.54 (13) |
N2—C8—H8A | 109.6 | F1—C23—S1 | 111.57 (13) |
C9—C8—H8A | 109.6 | F3—C23—S1 | 110.67 (12) |
N2—C8—H8B | 109.6 | F6—C24—F4 | 107.96 (16) |
C9—C8—H8B | 109.6 | F6—C24—F5 | 108.05 (17) |
H8A—C8—H8B | 108.1 | F4—C24—F5 | 106.62 (14) |
C14—C9—C10 | 119.20 (14) | F6—C24—S2 | 111.40 (13) |
C14—C9—C8 | 120.99 (14) | F4—C24—S2 | 111.95 (12) |
C10—C9—C8 | 119.73 (13) | F5—C24—S2 | 110.66 (12) |
C1—C2—C3—C4 | −179.15 (15) | C17—N4—C16—N3 | −0.59 (16) |
C7—N1—C4—C3 | 58.86 (19) | C19—N4—C16—N3 | 174.18 (13) |
C5—N1—C4—C3 | −120.77 (16) | C18—N3—C16—N4 | 1.04 (16) |
C2—C3—C4—N1 | 175.68 (13) | C15—N3—C16—N4 | 178.79 (13) |
C7—N1—C5—C6 | −0.35 (17) | C16—N4—C17—C18 | −0.09 (16) |
C4—N1—C5—C6 | 179.33 (14) | C19—N4—C17—C18 | −174.85 (13) |
N1—C5—C6—N2 | 0.31 (17) | N4—C17—C18—N3 | 0.71 (16) |
C7—N2—C6—C5 | −0.16 (17) | C16—N3—C18—C17 | −1.09 (16) |
C8—N2—C6—C5 | −171.61 (13) | C15—N3—C18—C17 | −178.86 (13) |
C5—N1—C7—N2 | 0.25 (17) | C16—N4—C19—C20 | −106.80 (15) |
C4—N1—C7—N2 | −179.43 (13) | C17—N4—C19—C20 | 67.12 (18) |
C6—N2—C7—N1 | −0.06 (16) | N4—C19—C20—C21 | 178.19 (12) |
C8—N2—C7—N1 | 171.35 (13) | C19—C20—C21—C22 | −67.24 (18) |
C7—N2—C8—C9 | −91.08 (17) | O3—S1—C23—F2 | 180.00 (12) |
C6—N2—C8—C9 | 78.95 (17) | O2—S1—C23—F2 | 59.16 (14) |
N2—C8—C9—C14 | −89.64 (17) | O1—S1—C23—F2 | −61.00 (13) |
N2—C8—C9—C10 | 87.09 (17) | O3—S1—C23—F1 | 59.26 (14) |
C14—C9—C10—C11 | 2.7 (2) | O2—S1—C23—F1 | −61.58 (14) |
C8—C9—C10—C11 | −174.04 (14) | O1—S1—C23—F1 | 178.26 (12) |
C9—C10—C11—C12 | −0.7 (2) | O3—S1—C23—F3 | −59.61 (16) |
C10—C11—C12—C13 | −1.9 (2) | O2—S1—C23—F3 | 179.55 (14) |
C10—C11—C12—C15 | 176.61 (14) | O1—S1—C23—F3 | 59.40 (16) |
C11—C12—C13—C14 | 2.4 (2) | O6—S2—C24—F6 | −175.94 (16) |
C15—C12—C13—C14 | −176.07 (14) | O4—S2—C24—F6 | 63.52 (17) |
C10—C9—C14—C13 | −2.2 (2) | O5—S2—C24—F6 | −56.14 (17) |
C8—C9—C14—C13 | 174.53 (15) | O6—S2—C24—F4 | 63.07 (14) |
C12—C13—C14—C9 | −0.4 (3) | O4—S2—C24—F4 | −57.48 (14) |
C16—N3—C15—C12 | −93.16 (17) | O5—S2—C24—F4 | −177.14 (12) |
C18—N3—C15—C12 | 84.23 (17) | O6—S2—C24—F5 | −55.71 (14) |
C11—C12—C15—N3 | 86.12 (16) | O4—S2—C24—F5 | −176.26 (12) |
C13—C12—C15—N3 | −95.39 (16) | O5—S2—C24—F5 | 64.08 (14) |
D—H···A | D—H | H···A | D···A | D—H···A |
C4—H4a···O3 | 0.99 | 2.50 | 3.397 (2) | 150 |
C5—H5···O2i | 0.95 | 2.46 | 3.243 (2) | 139 |
C6—H6···F1i | 0.95 | 2.45 | 3.261 (2) | 143 |
C6—H6···O4 | 0.95 | 2.44 | 3.166 (2) | 133 |
C7—H7···O1ii | 0.95 | 2.25 | 3.188 (2) | 168 |
C10—H10···F3ii | 0.95 | 2.47 | 3.365 (2) | 157 |
C16—H16···O5iii | 0.95 | 2.29 | 3.135 (2) | 147 |
C18—H18···O3iv | 0.95 | 2.46 | 2.956 (2) | 112 |
Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x+1, −y+1, −z+1; (iii) x, y−1, z; (iv) x, y, z+1. |
Experimental details
(I) | (II) | |
Crystal data | ||
Chemical formula | C16H20N42+·2BF4− | C22H32N42+·2CF3O3S− |
Mr | 441.98 | 650.66 |
Crystal system, space group | Monoclinic, P21/c | Triclinic, P1 |
Temperature (K) | 100 | 100 |
a, b, c (Å) | 4.9517 (2), 12.8674 (5), 15.2828 (6) | 10.3833 (1), 12.0470 (2), 13.6933 (2) |
α, β, γ (°) | 90, 92.806 (3), 90 | 100.752 (1), 105.194 (1), 111.970 (1) |
V (Å3) | 972.58 (7) | 1453.36 (4) |
Z | 2 | 2 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.14 | 0.27 |
Crystal size (mm) | 0.36 × 0.08 × 0.06 | 0.44 × 0.22 × 0.07 |
Data collection | ||
Diffractometer | Bruker SMART APEX diffractometer | Bruker SMART APEX diffractometer |
Absorption correction | – | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | – | 0.878, 0.982 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8044, 2231, 1364 | 18621, 6636, 5673 |
Rint | 0.075 | 0.035 |
(sin θ/λ)max (Å−1) | 0.650 | 0.650 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.050, 0.120, 1.02 | 0.035, 0.101, 1.02 |
No. of reflections | 2231 | 6636 |
No. of parameters | 137 | 379 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.24, −0.30 | 0.61, −0.53 |
Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2008).
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2···F1 | 0.95 | 2.59 | 3.367 (3) | 140 |
C3—H3···F2i | 0.95 | 2.33 | 3.272 (3) | 171 |
C4—H4···F3ii | 0.95 | 2.37 | 3.287 (3) | 162 |
C4—H4···F4ii | 0.95 | 2.48 | 3.278 (3) | 141 |
Symmetry codes: (i) −x, −y, −z+1; (ii) −x+1, y+1/2, −z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
C4—H4a···O3 | 0.99 | 2.50 | 3.397 (2) | 150 |
C5—H5···O2i | 0.95 | 2.46 | 3.243 (2) | 139 |
C6—H6···F1i | 0.95 | 2.45 | 3.261 (2) | 143 |
C6—H6···O4 | 0.95 | 2.44 | 3.166 (2) | 133 |
C7—H7···O1ii | 0.95 | 2.25 | 3.188 (2) | 168 |
C10—H10···F3ii | 0.95 | 2.47 | 3.365 (2) | 157 |
C16—H16···O5iii | 0.95 | 2.29 | 3.135 (2) | 147 |
C18—H18···O3iv | 0.95 | 2.46 | 2.956 (2) | 112 |
Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x+1, −y+1, −z+1; (iii) x, y−1, z; (iv) x, y, z+1. |
Acknowledgements
The authors thank the University of Malaya for financial support of this study (Research University grant Nos. TA 0009/2007 A and TA 0009/2008 A).
References
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Some ionic liquids incorporate an imidazolium group as this feature appears to confer limited crystallinity despite their homogenous appearance. An understanding of the liquid–crystalline state of such compounds has been provided by the crystal structure of the prototype ionic liquid 1-butyl-3-methylimidazolium chloride. The solid-state structures shows weak hydrogen bonds between the cations and chloride anions (Saha et al., 2003). A better understanding of the solid-state versus the liquid-state structures is furnished by the crystal structure of the hexafluorophosphate salt (Dibrov & Kochi, 2006). As the hexafluorophosphate anion does not normally participate in nonclassical hydrogen bonding, the crystal structure probably better represents the inter-ionic interactions of the liquid–crystalline state.
Our interest in the 3,3'-dimethyl-1,1'-(1,4-phenylenedimethylene)di-1H-imidazolium dication arises from several reports on the applications of this class of ionic liquids. For example, 1-n-butyl-3-methylimidazolium tetrafluoroborate possesses an excellent gas-absorption property. As other studies have suggested that the nature of the anion influences this property (Aki et al., 2004; Anthony et al., 2005; Galán Sánchez et al., 2007), we synthesized several 3,3'-dimethyl-1,1'-(1,4-phenylenedimethylene)di-1H-imidazolium salts, viz. with the hexafluorophosphate, tetrafluoroborate and trifluoromethylsulfonate anions, and examined their 13C NMR properties in various solvents (Ganesan & Alias, 2008). We expect this class of compounds, which possess a rigid phenylenedimethylene link between the imidazolium rings, to possess superior physical properties as studies on other compounds have shown the connection between chain length and physical properties (Holbrey & Seddon, 1999).
3,3'-Dimethyl-1,1'-(1,4-phenylenedimethylene)di-1H-imidazolium bis(tetrafluoroborate), (I), exists as a dication and a monoanion (Fig. 1) that interact weakly through C—H···F hydrogen bonding. The anion forms several contacts that are less than the sum of the van der Waals radii of hydrogen (1.2Å) and fluorine (1.5Å) (Table 1). Two of the three hydrogen bonds, from the imidazolium group, are significantly short (2.33 and 2.37Å); moreover, the two hydrogen bonds are almost linear (171 and 162°, respectively). All distances between adjacent phenylene rings or between adjacent imidazoliumyl rings exceed 4Å. The bond dimensions of the dication are similar to those found in the hexachloroplatinate(IV) (Li & Liu, 2003), tetrathiocyanatocadmate(II) (Liu et al., 2002), tetraselenocyanocadmate (Liu & Li, 2003) and tetrachloroargentate (Wang et al., 2005) salts.
The bond dimensions of the tetrafluoroborate counter-anions are marginally different from those found in more flexible dications, viz. 1,1'-methylenebis(3-methylimidazolium) dipicrate (Jin et al., 2006) and 3,3'-dimethyl-1,1'-ethylenediimidazolium dibromide (Jin et al., 2007). The N—Cmethylene distance [1.470 (3)Å] is lengthened compared with those [1.457 (2) and 1.458 (2)Å] found in the dipicrate salt and the N—Cethylene distance [1.461 (2)Å] found in the dibromide salt.
3,3'-Di-n-butyl-1,1'-(1,4-phenylenedimethylene)di-1H-imidazolium bis(trifluoromethanesulfonate), (II), also has the dication interacting with the monoanions (Fig. 2) through weak C—H···F hydrogen bonds. The imidazolium–phenylenedimethylene–imidazolium portion has a Z shape, with the butyl substituents at either ends. One of the butyl groups has the usual zigzag conformation, whereas the other has has a U conformation. The C—H···F interactions are somewhat longer and the hydrogen bonds more bent; however, two short linear C—H···O hydrogen bonds are present that are comparable with classical hydrogen bonds (Table 2).
In the present study, because the two anions do not engage in strong hydrogen bonding, the ionic liquid state then probably requires cation–anion interactions for long-range crystallinity.