


Supporting information
![]() | Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536808039639/hk2581sup1.cif |
![]() | Structure factor file (CIF format) https://doi.org/10.1107/S1600536808039639/hk2581Isup2.hkl |
CCDC reference: 713290
Key indicators
- Single-crystal X-ray study
- T = 298 K
- Mean
(C-C) = 0.007 Å
- Disorder in solvent or counterion
- R factor = 0.065
- wR factor = 0.166
- Data-to-parameter ratio = 10.1
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT340_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ... 7 PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical . ? PLAT154_ALERT_1_C The su's on the Cell Angles are Equal (x 10000) 3000 Deg. PLAT234_ALERT_4_C Large Hirshfeld Difference C1 -- C2 .. 0.12 Ang. PLAT244_ALERT_4_C Low 'Solvent' Ueq as Compared to Neighbors for P
Alert level G PLAT180_ALERT_4_G Check Cell Rounding: # of Values Ending with 0 = 3 PLAT302_ALERT_4_G Anion/Solvent Disorder ......................... 46.00 Perc.
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 5 ALERT level C = Check and explain 2 ALERT level G = General alerts; check 2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 0 ALERT type 2 Indicator that the structure model may be wrong or deficient 1 ALERT type 3 Indicator that the structure quality may be low 4 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
For the preparation of the title compound, 1,6-dibromide hexane (12.2 g, 0.05 mol) was added to acetonitrile solution (50 ml) of dehydrate pyridine (7.91 g, 0.10 mol) at 353 K. After stirring for 24 h, the mixture was cooled to room temperature and filtered. The solid was washed with ethyl acetate and dried. Then, the solid (2.01 g, 5 mmol) was dissolved in distilled water (50 ml) and potassium hexafluorophosphate (1.84 g, 10 mmol) was added. After stirring at room temperature for 3 h, the colorless solid formed was collected by filtration, washed with distilled water (50 ml) and dried. The product was purified by repeated crystallization. Crystals suitable for X-ray analysis were obtained by slow evaporation of acetone (yield; 3.08 g, 80%, m.p. 513 K).
The F1, F2, F3, F4, F5 and F6 atoms in hexafluorophosphate were disordered over two positions. During the refinement process the disordered atoms were refined with occupancies of 0.43 (2) for F1, F2, F3, F4, F5 , F6 and 0.57 (2) for F1', F2', F3', F4', F5', F6', respectively. H atoms were positioned geometrically, with C-H = 0.93 and 0.97 Å for aromatic and methylene H, respectively, and constrained to ride on their parent atoms with Uiso(H) = 1.2Ueq(C).
Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell refinement: CAD-4 Software (Enraf–Nonius, 1989); data reduction: XCAD4 (Harms & Wocadlo, 1995); 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).
C16H22N22+·2PF6− | Z = 1 |
Mr = 532.30 (3) | F(000) = 270 |
Triclinic, P1 | Dx = 1.545 Mg m−3 |
Hall symbol: -P 1 | Melting point: 513 K |
a = 7.9140 (16) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 9.2930 (18) Å | Cell parameters from 25 reflections |
c = 9.4870 (19) Å | θ = 10–12° |
α = 65.13 (3)° | µ = 0.29 mm−1 |
β = 65.46 (3)° | T = 298 K |
γ = 74.37 (3)° | Block, colorless |
V = 572.0 (3) Å3 | 0.30 × 0.30 × 0.20 mm |
Enraf–Nonius CAD-4 diffractometer | 1499 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.047 |
Graphite monochromator | θmax = 25.1°, θmin = 2.4° |
ω/2θ scans | h = −8→9 |
Absorption correction: ψ scan (North et al., 1968) | k = −9→10 |
Tmin = 0.917, Tmax = 0.944 | l = 0→11 |
2172 measured reflections | 3 standard reflections every 120 min |
2014 independent reflections | intensity decay: none |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.065 | H-atom parameters constrained |
wR(F2) = 0.166 | w = 1/[σ2(Fo2) + (0.06P)2 + 0.95P] where P = (Fo2 + 2Fc2)/3 |
S = 1.01 | (Δ/σ)max < 0.001 |
2014 reflections | Δρmax = 0.30 e Å−3 |
200 parameters | Δρmin = −0.38 e Å−3 |
Primary atom site location: structure-invariant direct methods |
C16H22N22+·2PF6− | γ = 74.37 (3)° |
Mr = 532.30 (3) | V = 572.0 (3) Å3 |
Triclinic, P1 | Z = 1 |
a = 7.9140 (16) Å | Mo Kα radiation |
b = 9.2930 (18) Å | µ = 0.29 mm−1 |
c = 9.4870 (19) Å | T = 298 K |
α = 65.13 (3)° | 0.30 × 0.30 × 0.20 mm |
β = 65.46 (3)° |
Enraf–Nonius CAD-4 diffractometer | 1499 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.047 |
Tmin = 0.917, Tmax = 0.944 | 3 standard reflections every 120 min |
2172 measured reflections | intensity decay: none |
2014 independent reflections |
R[F2 > 2σ(F2)] = 0.065 | 200 parameters |
wR(F2) = 0.166 | H-atom parameters constrained |
S = 1.01 | Δρmax = 0.30 e Å−3 |
2014 reflections | Δρmin = −0.38 e Å−3 |
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. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
P | 0.16995 (14) | 0.79005 (13) | 0.78487 (13) | 0.0539 (4) | |
N | 0.6355 (4) | 0.7536 (4) | 0.2462 (4) | 0.0472 (8) | |
F1 | −0.006 (3) | 0.696 (3) | 0.842 (2) | 0.156 (6) | 0.43 (2) |
F2 | 0.369 (2) | 0.8457 (19) | 0.721 (2) | 0.104 (5) | 0.43 (2) |
F3 | 0.034 (2) | 0.8894 (16) | 0.8982 (15) | 0.091 (4) | 0.43 (2) |
F4 | 0.215 (2) | 0.645 (2) | 0.939 (2) | 0.076 (4) | 0.43 (2) |
F5 | 0.126 (2) | 0.936 (2) | 0.635 (2) | 0.078 (4) | 0.43 (2) |
F6 | 0.223 (3) | 0.677 (3) | 0.684 (2) | 0.076 (4) | 0.43 (2) |
F1' | −0.0338 (9) | 0.7809 (16) | 0.8155 (14) | 0.118 (4) | 0.57 (2) |
F2' | 0.375 (2) | 0.785 (2) | 0.775 (2) | 0.144 (5) | 0.57 (2) |
F3' | 0.127 (2) | 0.9036 (12) | 0.8910 (13) | 0.098 (3) | 0.57 (2) |
F4' | 0.150 (2) | 0.6338 (18) | 0.9501 (17) | 0.090 (4) | 0.57 (2) |
F5' | 0.195 (2) | 0.9495 (17) | 0.6211 (17) | 0.094 (4) | 0.57 (2) |
F6' | 0.2820 (19) | 0.6854 (19) | 0.6687 (18) | 0.082 (4) | 0.57 (2) |
C1 | 0.6255 (6) | 0.6893 (5) | 0.1468 (5) | 0.0607 (11) | |
H1A | 0.7227 | 0.6159 | 0.1113 | 0.073* | |
C2 | 0.4732 (7) | 0.7312 (6) | 0.0972 (6) | 0.0735 (13) | |
H2A | 0.4661 | 0.6866 | 0.0288 | 0.088* | |
C3 | 0.3292 (6) | 0.8420 (6) | 0.1517 (6) | 0.0751 (14) | |
H3A | 0.2260 | 0.8736 | 0.1179 | 0.090* | |
C4 | 0.3402 (6) | 0.9030 (6) | 0.2537 (6) | 0.0721 (13) | |
H4A | 0.2428 | 0.9751 | 0.2913 | 0.087* | |
C5 | 0.4934 (5) | 0.8603 (5) | 0.3029 (5) | 0.0543 (10) | |
H5A | 0.5003 | 0.9029 | 0.3730 | 0.065* | |
C6 | 0.7977 (5) | 0.7070 (5) | 0.3014 (5) | 0.0580 (10) | |
H6A | 0.8387 | 0.8022 | 0.2896 | 0.070* | |
H6B | 0.8998 | 0.6558 | 0.2307 | 0.070* | |
C7 | 0.7536 (5) | 0.5942 (5) | 0.4801 (5) | 0.0563 (10) | |
H7A | 0.7184 | 0.4969 | 0.4908 | 0.068* | |
H7B | 0.6475 | 0.6434 | 0.5502 | 0.068* | |
C8 | 0.9189 (5) | 0.5519 (5) | 0.5406 (5) | 0.0602 (11) | |
H8A | 0.9628 | 0.6498 | 0.5183 | 0.072* | |
H8B | 0.8761 | 0.4963 | 0.6595 | 0.072* |
U11 | U22 | U33 | U12 | U13 | U23 | |
P | 0.0470 (6) | 0.0550 (6) | 0.0538 (6) | 0.0051 (4) | −0.0114 (5) | −0.0263 (5) |
N | 0.0332 (15) | 0.0466 (17) | 0.0475 (17) | −0.0002 (13) | −0.0093 (13) | −0.0107 (14) |
F1 | 0.136 (9) | 0.160 (11) | 0.165 (9) | −0.050 (8) | −0.033 (7) | −0.049 (8) |
F2 | 0.082 (6) | 0.104 (7) | 0.133 (9) | −0.045 (5) | −0.035 (6) | −0.030 (6) |
F3 | 0.101 (8) | 0.077 (5) | 0.074 (5) | 0.016 (5) | −0.007 (5) | −0.048 (4) |
F4 | 0.085 (8) | 0.067 (5) | 0.077 (7) | −0.003 (6) | −0.043 (6) | −0.016 (4) |
F5 | 0.070 (6) | 0.080 (7) | 0.059 (5) | 0.015 (5) | −0.024 (5) | −0.015 (4) |
F6 | 0.097 (9) | 0.078 (5) | 0.083 (8) | −0.014 (6) | −0.038 (7) | −0.046 (5) |
F1' | 0.041 (3) | 0.113 (7) | 0.173 (7) | −0.002 (3) | −0.039 (3) | −0.027 (5) |
F2' | 0.118 (6) | 0.180 (10) | 0.147 (8) | −0.033 (7) | −0.069 (6) | −0.036 (7) |
F3' | 0.126 (7) | 0.088 (4) | 0.086 (4) | 0.000 (5) | −0.021 (5) | −0.058 (3) |
F4' | 0.090 (7) | 0.068 (4) | 0.074 (4) | 0.010 (5) | −0.009 (5) | −0.022 (3) |
F5' | 0.124 (8) | 0.077 (4) | 0.069 (4) | −0.014 (6) | −0.023 (6) | −0.023 (3) |
F6' | 0.074 (6) | 0.078 (5) | 0.075 (4) | 0.002 (4) | 0.003 (4) | −0.043 (3) |
C1 | 0.064 (3) | 0.052 (2) | 0.057 (2) | 0.0000 (19) | −0.015 (2) | −0.022 (2) |
C2 | 0.084 (3) | 0.086 (3) | 0.066 (3) | −0.017 (3) | −0.040 (3) | −0.023 (3) |
C3 | 0.051 (3) | 0.095 (4) | 0.066 (3) | −0.015 (2) | −0.031 (2) | −0.002 (3) |
C4 | 0.042 (2) | 0.083 (3) | 0.066 (3) | 0.014 (2) | −0.014 (2) | −0.021 (2) |
C5 | 0.050 (2) | 0.056 (2) | 0.053 (2) | 0.0118 (18) | −0.0171 (18) | −0.0268 (19) |
C6 | 0.0340 (19) | 0.066 (3) | 0.066 (3) | −0.0019 (17) | −0.0187 (18) | −0.017 (2) |
C7 | 0.0339 (19) | 0.074 (3) | 0.057 (2) | 0.0055 (18) | −0.0156 (17) | −0.027 (2) |
C8 | 0.044 (2) | 0.082 (3) | 0.060 (2) | 0.009 (2) | −0.0230 (19) | −0.035 (2) |
P—F1' | 1.535 (7) | C3—C4 | 1.350 (7) |
P—F6 | 1.567 (19) | C3—H3A | 0.9300 |
P—F2' | 1.575 (15) | C4—C5 | 1.379 (6) |
P—F3 | 1.582 (11) | C4—H4A | 0.9300 |
P—F2 | 1.583 (14) | C5—N | 1.372 (5) |
P—F5 | 1.588 (16) | C5—H5A | 0.9300 |
P—F6' | 1.604 (14) | N—C6 | 1.476 (5) |
P—F4' | 1.611 (14) | C6—C7 | 1.518 (6) |
P—F4 | 1.612 (18) | C6—H6A | 0.9700 |
P—F5' | 1.617 (14) | C6—H6B | 0.9700 |
P—F1 | 1.619 (15) | C7—C8 | 1.534 (5) |
P—F3' | 1.631 (9) | C7—H7A | 0.9700 |
C1—N | 1.347 (5) | C7—H7B | 0.9700 |
C1—C2 | 1.375 (6) | C8—C8i | 1.518 (7) |
C1—H1A | 0.9300 | C8—H8A | 0.9700 |
C2—C3 | 1.397 (7) | C8—H8B | 0.9700 |
C2—H2A | 0.9300 | ||
F1'—P—F6 | 85.7 (10) | F4—P—F1 | 83.6 (8) |
F1'—P—F2' | 173.4 (6) | F5'—P—F1 | 116.5 (8) |
F6—P—F2' | 95.7 (10) | F1'—P—F3' | 97.5 (6) |
F1'—P—F3 | 70.4 (7) | F6—P—F3' | 176.5 (11) |
F6—P—F3 | 156.1 (13) | F2'—P—F3' | 80.9 (7) |
F2'—P—F3 | 107.8 (9) | F2—P—F3' | 78.8 (9) |
F1'—P—F2 | 164.7 (6) | F5—P—F3' | 92.5 (8) |
F6—P—F2 | 98.4 (9) | F6'—P—F3' | 160.7 (10) |
F3—P—F2 | 105.1 (10) | F4'—P—F3' | 90.4 (7) |
F1'—P—F5 | 76.2 (6) | F4—P—F3' | 86.1 (8) |
F6—P—F5 | 89.5 (10) | F5'—P—F3' | 88.0 (6) |
F2'—P—F5 | 110.2 (6) | F1—P—F3' | 112.6 (7) |
F3—P—F5 | 86.5 (8) | N—C1—C2 | 120.6 (4) |
F2—P—F5 | 89.1 (7) | N—C1—H1A | 119.7 |
F1'—P—F6' | 101.7 (9) | C2—C1—H1A | 119.7 |
F2'—P—F6' | 80.1 (9) | C1—C2—C3 | 118.7 (4) |
F3—P—F6' | 172.1 (12) | C1—C2—H2A | 120.7 |
F2—P—F6' | 82.4 (8) | C3—C2—H2A | 120.7 |
F5—P—F6' | 91.2 (9) | C4—C3—C2 | 119.8 (4) |
F1'—P—F4' | 86.0 (5) | C4—C3—H3A | 120.1 |
F6—P—F4' | 88.5 (9) | C2—C3—H3A | 120.1 |
F2'—P—F4' | 87.5 (6) | C3—C4—C5 | 121.1 (4) |
F3—P—F4' | 88.2 (7) | C3—C4—H4A | 119.4 |
F2—P—F4' | 108.7 (6) | C5—C4—H4A | 119.4 |
F5—P—F4' | 162.2 (6) | N—C5—C4 | 118.6 (4) |
F6'—P—F4' | 91.8 (7) | N—C5—H5A | 120.7 |
F1'—P—F4 | 104.3 (6) | C4—C5—H5A | 120.7 |
F6—P—F4 | 91.8 (10) | C1—N—C5 | 121.2 (3) |
F2'—P—F4 | 69.2 (7) | C1—N—C6 | 120.7 (3) |
F3—P—F4 | 92.5 (9) | C5—N—C6 | 118.1 (3) |
F2—P—F4 | 90.3 (7) | N—C6—C7 | 112.5 (3) |
F5—P—F4 | 178.6 (11) | N—C6—H6A | 109.1 |
F6'—P—F4 | 90.0 (9) | C7—C6—H6A | 109.1 |
F1'—P—F5' | 95.7 (6) | N—C6—H6B | 109.1 |
F6—P—F5' | 93.0 (9) | C7—C6—H6B | 109.1 |
F2'—P—F5' | 90.7 (6) | H6A—C6—H6B | 107.8 |
F3—P—F5' | 91.0 (7) | C6—C7—C8 | 112.7 (3) |
F2—P—F5' | 69.5 (6) | C6—C7—H7A | 109.0 |
F6'—P—F5' | 89.2 (8) | C8—C7—H7A | 109.0 |
F4'—P—F5' | 177.8 (7) | C6—C7—H7B | 109.0 |
F4—P—F5' | 159.8 (6) | C8—C7—H7B | 109.0 |
F6—P—F1 | 69.9 (12) | H7A—C7—H7B | 107.8 |
F2'—P—F1 | 149.1 (8) | C8i—C8—C7 | 113.4 (4) |
F3—P—F1 | 87.2 (7) | C8i—C8—H8A | 108.9 |
F2—P—F1 | 166.6 (10) | C7—C8—H8A | 108.9 |
F5—P—F1 | 97.2 (9) | C8i—C8—H8B | 108.9 |
F6'—P—F1 | 85.7 (11) | C7—C8—H8B | 108.9 |
F4'—P—F1 | 65.6 (7) | H8A—C8—H8B | 107.7 |
Symmetry code: (i) −x+2, −y+1, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
C1—H1A···F4′ii | 0.93 | 2.48 | 3.333 (17) | 153 |
C2—H2A···F2′iii | 0.93 | 2.53 | 3.267 (18) | 137 |
C3—H3A···F3′iii | 0.93 | 2.47 | 3.257 (15) | 142 |
C4—H4A···F1′iv | 0.93 | 2.52 | 3.287 (14) | 140 |
Symmetry codes: (ii) −x+1, −y+1, −z+1; (iii) x, y, z−1; (iv) −x, −y+2, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C16H22N22+·2PF6− |
Mr | 532.30 (3) |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 298 |
a, b, c (Å) | 7.9140 (16), 9.2930 (18), 9.4870 (19) |
α, β, γ (°) | 65.13 (3), 65.46 (3), 74.37 (3) |
V (Å3) | 572.0 (3) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 0.29 |
Crystal size (mm) | 0.30 × 0.30 × 0.20 |
Data collection | |
Diffractometer | Enraf–Nonius CAD-4 diffractometer |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.917, 0.944 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2172, 2014, 1499 |
Rint | 0.047 |
(sin θ/λ)max (Å−1) | 0.598 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.065, 0.166, 1.01 |
No. of reflections | 2014 |
No. of parameters | 200 |
No. of restraints | ? |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.30, −0.38 |
Computer programs: CAD-4 Software (Enraf–Nonius, 1989), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
D—H···A | D—H | H···A | D···A | D—H···A |
C1—H1A···F4'i | 0.93 | 2.48 | 3.333 (17) | 153.00 |
C2—H2A···F2'ii | 0.93 | 2.53 | 3.267 (18) | 137.00 |
C3—H3A···F3'ii | 0.93 | 2.47 | 3.257 (15) | 142.00 |
C4—H4A···F1'iii | 0.93 | 2.52 | 3.287 (14) | 140.00 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x, y, z−1; (iii) −x, −y+2, −z+1. |
The title compound is a dicationic ionic liquid, which has high thermal stability. Applications of the dicationic ionic liquid are found in biochemistry as well as many areas of chemistry (Jared et al., 2005). We report herein the crystal structure of the title compound.
The asymmetric unit of the title compound (Fig. 1) contains one-half molecule and a hexafluorophosphate molecule, where the bond lengths (Allen et al., 1987) and angles are within normal ranges.
In the crystal structure, intermolecular C-H···F hydrogen bonds (Table 1) link the molecules (Fig. 2), in which they may be effective in the stabilization of the structure.