Acta Cryst. (2009). E65, o2972 [ doi:10.1107/S1600536809045115 ]
In the title Schiff base compound, C13H14Cl2N3+·PF6-, the dihedral angle between the aromatic ring and imidazole ring in the cation is 6.10 (2)°. Intermolecular C-H
F hydrogen-bonding interactions and ![[pi]](/logos/entities/pi_rmgif.gif)
- stacking interactions [centoid-centroid distance = 3.7203 (12) Å] help stabilize the crystal packing.
A mixture of the ionic liquid 1-(2-aminoethyl)-3-methylimidazolium hexafluorophosphate (4 mmol) and 2,4-dichlorobenzaldehyde (3 mmol) was stirred for 4 h at room temperature under solvent-free conditions. After completion ofthe reaction, ethanol (30 ml) was added to the reaction mixture, filtered off the solid product and washed with cold ethanol. The crude product was purified by recrystallization in ethanol/ethyl acetate(3:1 v/v). Single crystals suitable for X-ray diffraction were obtained by slow evaporation of an ethyl acetate solution of the complex at room temperature.
All H atoms were located in a difference Fourier maps and were refined as ridingatoms: C—H = 0.95–0.99 Å and with Uiso(H) = 1.2 Ueq(C).
Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); 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).
![[Figure 1]](./jj2012fig1thm.gif)
| Fig. 1. The molecular structure of the title compound in (I) showing the atom numbering Scheme. Displacement ellipsoids are drawn at the 50% probability level. |
![[Figure 2]](./jj2012fig2thm.gif)
| Fig. 2. Packing diagram of (I) viewed down the b axis. Weak C–H···Cl intramolecular and C–H···F intermolecular hydrogen bonding interactions are shown as dashed lines. |
| C13H14Cl2N3+·PF6− | Z = 2 |
| Mr = 428.14 | F(000) = 432 |
| Triclinic, P1 | Dx = 1.702 Mg m−3 |
| Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
| a = 8.3465 (13) Å | Cell parameters from 5376 reflections |
| b = 10.1419 (16) Å | θ = 2.7–27.0° |
| c = 11.0310 (17) Å | µ = 0.55 mm−1 |
| α = 78.899 (2)° | T = 173 K |
| β = 76.523 (2)° | Block, colorless |
| γ = 67.834 (2)° | 0.32 × 0.24 × 0.21 mm |
| V = 835.3 (2) Å3 |
| Bruker SMART CCD area-detector diffractometer | 3566 independent reflections |
| Radiation source: fine-focus sealed tube | 3151 reflections with I > 2σ(I) |
| graphite | Rint = 0.0000 |
| φ and ω scans | θmax = 27.0°, θmin = 1.9° |
| Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −10→10 |
| Tmin = 0.844, Tmax = 0.894 | k = −12→12 |
| 3566 measured reflections | l = −14→13 |
| 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)] = 0.031 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.093 | H-atom parameters constrained |
| S = 1.10 | w = 1/[σ2(Fo2) + (0.047P)2 + 0.3955P] where P = (Fo2 + 2Fc2)/3 |
| 3566 reflections | (Δ/σ)max = 0.001 |
| 227 parameters | Δρmax = 0.25 e Å−3 |
| 0 restraints | Δρmin = −0.34 e Å−3 |
| C13H14Cl2N3+·PF6− | γ = 67.834 (2)° |
| Mr = 428.14 | V = 835.3 (2) Å3 |
| Triclinic, P1 | Z = 2 |
| a = 8.3465 (13) Å | Mo Kα radiation |
| b = 10.1419 (16) Å | µ = 0.55 mm−1 |
| c = 11.0310 (17) Å | T = 173 K |
| α = 78.899 (2)° | 0.32 × 0.24 × 0.21 mm |
| β = 76.523 (2)° |
| Bruker SMART CCD area-detector diffractometer | 3566 independent reflections |
| Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 3151 reflections with I > 2σ(I) |
| Tmin = 0.844, Tmax = 0.894 | Rint = 0.0000 |
| 3566 measured reflections | θmax = 27.0° |
| R[F2 > 2σ(F2)] = 0.031 | H-atom parameters constrained |
| wR(F2) = 0.093 | Δρmax = 0.25 e Å−3 |
| S = 1.10 | Δρmin = −0.34 e Å−3 |
| 3566 reflections | Absolute structure: ? |
| 227 parameters | Flack parameter: ? |
| 0 restraints | Rogers parameter: ? |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 | ||
| C1 | 0.3066 (2) | 0.34376 (17) | 0.75848 (15) | 0.0220 (3) | |
| C2 | 0.3555 (2) | 0.30042 (17) | 0.87666 (15) | 0.0227 (3) | |
| C3 | 0.4986 (2) | 0.17904 (17) | 0.90058 (15) | 0.0241 (3) | |
| H3 | 0.5296 | 0.1513 | 0.9817 | 0.029* | |
| C4 | 0.5944 (2) | 0.09983 (17) | 0.80205 (16) | 0.0240 (3) | |
| C5 | 0.5499 (2) | 0.13684 (18) | 0.68374 (16) | 0.0270 (3) | |
| H5 | 0.6167 | 0.0796 | 0.6180 | 0.032* | |
| C6 | 0.4071 (2) | 0.25808 (18) | 0.66287 (15) | 0.0257 (3) | |
| H6 | 0.3761 | 0.2841 | 0.5818 | 0.031* | |
| C7 | 0.1562 (2) | 0.47512 (17) | 0.73301 (15) | 0.0237 (3) | |
| H7 | 0.0901 | 0.5323 | 0.7989 | 0.028* | |
| C8 | −0.0351 (2) | 0.64629 (18) | 0.61084 (16) | 0.0283 (4) | |
| H8A | −0.0911 | 0.6807 | 0.6939 | 0.034* | |
| H8B | −0.1235 | 0.6282 | 0.5765 | 0.034* | |
| C9 | 0.0251 (2) | 0.76060 (18) | 0.52316 (16) | 0.0297 (4) | |
| H9A | −0.0739 | 0.8533 | 0.5247 | 0.036* | |
| H9B | 0.1211 | 0.7719 | 0.5539 | 0.036* | |
| C10 | 0.0061 (2) | 0.79621 (17) | 0.29722 (15) | 0.0244 (3) | |
| H10 | −0.1003 | 0.8765 | 0.3020 | 0.029* | |
| C11 | 0.2433 (2) | 0.62263 (18) | 0.22472 (17) | 0.0295 (4) | |
| H11 | 0.3313 | 0.5609 | 0.1688 | 0.035* | |
| C12 | 0.2369 (2) | 0.61583 (18) | 0.34869 (17) | 0.0285 (4) | |
| H12 | 0.3197 | 0.5483 | 0.3968 | 0.034* | |
| C13 | 0.0537 (3) | 0.7880 (2) | 0.06825 (17) | 0.0368 (4) | |
| H13A | −0.0631 | 0.8627 | 0.0741 | 0.055* | |
| H13B | 0.0539 | 0.7081 | 0.0304 | 0.055* | |
| H13C | 0.1410 | 0.8276 | 0.0161 | 0.055* | |
| Cl1 | 0.23667 (6) | 0.39837 (5) | 1.00213 (4) | 0.03149 (12) | |
| Cl2 | 0.78059 (6) | −0.04833 (5) | 0.82692 (4) | 0.03387 (13) | |
| F1 | 0.44475 (17) | 0.19348 (17) | 0.31806 (17) | 0.0655 (4) | |
| F2 | 0.58081 (16) | 0.32801 (12) | 0.36186 (12) | 0.0436 (3) | |
| F3 | 0.70635 (18) | 0.08681 (13) | 0.38373 (11) | 0.0492 (3) | |
| F4 | 0.82315 (14) | 0.21845 (14) | 0.22679 (11) | 0.0412 (3) | |
| F5 | 0.68843 (16) | 0.08228 (12) | 0.18313 (11) | 0.0423 (3) | |
| F6 | 0.56548 (19) | 0.32368 (14) | 0.15939 (13) | 0.0555 (4) | |
| N1 | 0.08759 (18) | 0.72527 (14) | 0.39294 (13) | 0.0243 (3) | |
| N2 | 0.09752 (19) | 0.73655 (15) | 0.19419 (13) | 0.0262 (3) | |
| N3 | 0.11363 (19) | 0.51306 (15) | 0.62537 (13) | 0.0263 (3) | |
| P1 | 0.63280 (5) | 0.20636 (5) | 0.27210 (4) | 0.02671 (12) |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| C1 | 0.0223 (7) | 0.0219 (8) | 0.0212 (7) | −0.0075 (6) | −0.0039 (6) | −0.0016 (6) |
| C2 | 0.0239 (7) | 0.0235 (8) | 0.0204 (7) | −0.0080 (6) | −0.0019 (6) | −0.0049 (6) |
| C3 | 0.0259 (8) | 0.0241 (8) | 0.0227 (8) | −0.0088 (6) | −0.0070 (6) | −0.0002 (6) |
| C4 | 0.0216 (7) | 0.0178 (7) | 0.0298 (8) | −0.0042 (6) | −0.0047 (6) | −0.0016 (6) |
| C5 | 0.0284 (8) | 0.0242 (8) | 0.0259 (8) | −0.0062 (7) | −0.0016 (6) | −0.0070 (6) |
| C6 | 0.0280 (8) | 0.0272 (8) | 0.0204 (7) | −0.0075 (7) | −0.0048 (6) | −0.0027 (6) |
| C7 | 0.0235 (8) | 0.0223 (8) | 0.0233 (8) | −0.0057 (6) | −0.0038 (6) | −0.0031 (6) |
| C8 | 0.0278 (8) | 0.0279 (9) | 0.0233 (8) | −0.0011 (7) | −0.0079 (6) | −0.0032 (6) |
| C9 | 0.0379 (9) | 0.0236 (8) | 0.0257 (8) | −0.0038 (7) | −0.0120 (7) | −0.0050 (6) |
| C10 | 0.0256 (8) | 0.0197 (7) | 0.0260 (8) | −0.0053 (6) | −0.0062 (6) | −0.0019 (6) |
| C11 | 0.0259 (8) | 0.0229 (8) | 0.0361 (9) | −0.0073 (7) | 0.0005 (7) | −0.0053 (7) |
| C12 | 0.0217 (8) | 0.0223 (8) | 0.0373 (9) | −0.0034 (6) | −0.0060 (7) | −0.0013 (7) |
| C13 | 0.0491 (11) | 0.0397 (10) | 0.0220 (8) | −0.0165 (9) | −0.0065 (8) | −0.0017 (7) |
| Cl1 | 0.0345 (2) | 0.0313 (2) | 0.0223 (2) | −0.00086 (17) | −0.00639 (16) | −0.00879 (16) |
| Cl2 | 0.0295 (2) | 0.0252 (2) | 0.0392 (2) | 0.00147 (16) | −0.00988 (17) | −0.00417 (17) |
| F1 | 0.0325 (7) | 0.0723 (10) | 0.0967 (12) | −0.0247 (7) | 0.0080 (7) | −0.0315 (9) |
| F2 | 0.0411 (6) | 0.0347 (6) | 0.0488 (7) | −0.0033 (5) | −0.0004 (5) | −0.0202 (5) |
| F3 | 0.0676 (9) | 0.0348 (6) | 0.0269 (6) | −0.0002 (6) | −0.0056 (5) | −0.0010 (5) |
| F4 | 0.0279 (6) | 0.0566 (7) | 0.0404 (6) | −0.0150 (5) | 0.0001 (5) | −0.0158 (5) |
| F5 | 0.0519 (7) | 0.0373 (6) | 0.0390 (6) | −0.0120 (5) | −0.0087 (5) | −0.0140 (5) |
| F6 | 0.0626 (9) | 0.0399 (7) | 0.0548 (8) | 0.0017 (6) | −0.0332 (7) | 0.0033 (6) |
| N1 | 0.0253 (7) | 0.0194 (6) | 0.0269 (7) | −0.0046 (5) | −0.0080 (5) | −0.0027 (5) |
| N2 | 0.0282 (7) | 0.0245 (7) | 0.0249 (7) | −0.0092 (6) | −0.0028 (5) | −0.0028 (5) |
| N3 | 0.0277 (7) | 0.0235 (7) | 0.0244 (7) | −0.0038 (6) | −0.0072 (5) | −0.0024 (5) |
| P1 | 0.0213 (2) | 0.0254 (2) | 0.0292 (2) | −0.00174 (17) | −0.00511 (16) | −0.00594 (17) |
| C1—C2 | 1.397 (2) | C9—H9B | 0.9900 |
| C1—C6 | 1.401 (2) | C10—N2 | 1.324 (2) |
| C1—C7 | 1.479 (2) | C10—N1 | 1.330 (2) |
| C2—C3 | 1.387 (2) | C10—H10 | 0.9500 |
| C2—Cl1 | 1.7414 (16) | C11—C12 | 1.345 (3) |
| C3—C4 | 1.383 (2) | C11—N2 | 1.382 (2) |
| C3—H3 | 0.9500 | C11—H11 | 0.9500 |
| C4—C5 | 1.383 (2) | C12—N1 | 1.380 (2) |
| C4—Cl2 | 1.7394 (16) | C12—H12 | 0.9500 |
| C5—C6 | 1.378 (2) | C13—N2 | 1.466 (2) |
| C5—H5 | 0.9500 | C13—H13A | 0.9800 |
| C6—H6 | 0.9500 | C13—H13B | 0.9800 |
| C7—N3 | 1.266 (2) | C13—H13C | 0.9800 |
| C7—H7 | 0.9500 | F1—P1 | 1.5798 (13) |
| C8—N3 | 1.462 (2) | F2—P1 | 1.5991 (12) |
| C8—C9 | 1.521 (3) | F3—P1 | 1.6059 (12) |
| C8—H8A | 0.9900 | F4—P1 | 1.5945 (12) |
| C8—H8B | 0.9900 | F5—P1 | 1.6077 (12) |
| C9—N1 | 1.474 (2) | F6—P1 | 1.5903 (13) |
| C9—H9A | 0.9900 | ||
| C2—C1—C6 | 117.32 (15) | N1—C10—H10 | 125.6 |
| C2—C1—C7 | 122.19 (14) | C12—C11—N2 | 106.95 (15) |
| C6—C1—C7 | 120.49 (14) | C12—C11—H11 | 126.5 |
| C3—C2—C1 | 122.51 (15) | N2—C11—H11 | 126.5 |
| C3—C2—Cl1 | 116.75 (12) | C11—C12—N1 | 107.24 (15) |
| C1—C2—Cl1 | 120.74 (12) | C11—C12—H12 | 126.4 |
| C4—C3—C2 | 117.56 (15) | N1—C12—H12 | 126.4 |
| C4—C3—H3 | 121.2 | N2—C13—H13A | 109.5 |
| C2—C3—H3 | 121.2 | N2—C13—H13B | 109.5 |
| C3—C4—C5 | 122.21 (15) | H13A—C13—H13B | 109.5 |
| C3—C4—Cl2 | 118.75 (13) | N2—C13—H13C | 109.5 |
| C5—C4—Cl2 | 119.02 (13) | H13A—C13—H13C | 109.5 |
| C6—C5—C4 | 118.87 (15) | H13B—C13—H13C | 109.5 |
| C6—C5—H5 | 120.6 | C10—N1—C12 | 108.39 (14) |
| C4—C5—H5 | 120.6 | C10—N1—C9 | 124.53 (14) |
| C5—C6—C1 | 121.51 (15) | C12—N1—C9 | 127.08 (14) |
| C5—C6—H6 | 119.2 | C10—N2—C11 | 108.67 (14) |
| C1—C6—H6 | 119.2 | C10—N2—C13 | 125.07 (15) |
| N3—C7—C1 | 121.45 (15) | C11—N2—C13 | 126.20 (15) |
| N3—C7—H7 | 119.3 | C7—N3—C8 | 116.53 (14) |
| C1—C7—H7 | 119.3 | F1—P1—F6 | 91.02 (9) |
| N3—C8—C9 | 110.67 (14) | F1—P1—F4 | 179.50 (9) |
| N3—C8—H8A | 109.5 | F6—P1—F4 | 89.48 (8) |
| C9—C8—H8A | 109.5 | F1—P1—F2 | 90.12 (7) |
| N3—C8—H8B | 109.5 | F6—P1—F2 | 91.08 (7) |
| C9—C8—H8B | 109.5 | F4—P1—F2 | 89.81 (6) |
| H8A—C8—H8B | 108.1 | F1—P1—F3 | 90.46 (9) |
| N1—C9—C8 | 112.47 (14) | F6—P1—F3 | 178.38 (8) |
| N1—C9—H9A | 109.1 | F4—P1—F3 | 89.04 (7) |
| C8—C9—H9A | 109.1 | F2—P1—F3 | 89.56 (7) |
| N1—C9—H9B | 109.1 | F1—P1—F5 | 90.54 (7) |
| C8—C9—H9B | 109.1 | F6—P1—F5 | 89.83 (7) |
| H9A—C9—H9B | 107.8 | F4—P1—F5 | 89.52 (6) |
| N2—C10—N1 | 108.75 (14) | F2—P1—F5 | 178.86 (7) |
| N2—C10—H10 | 125.6 | F3—P1—F5 | 89.51 (7) |
| C6—C1—C2—C3 | 0.9 (2) | N3—C8—C9—N1 | 67.10 (18) |
| C7—C1—C2—C3 | −178.59 (15) | N2—C11—C12—N1 | 0.05 (19) |
| C6—C1—C2—Cl1 | −179.03 (12) | N2—C10—N1—C12 | −0.11 (18) |
| C7—C1—C2—Cl1 | 1.5 (2) | N2—C10—N1—C9 | 179.91 (15) |
| C1—C2—C3—C4 | 0.0 (2) | C11—C12—N1—C10 | 0.03 (19) |
| Cl1—C2—C3—C4 | 179.95 (12) | C11—C12—N1—C9 | −179.99 (16) |
| C2—C3—C4—C5 | −1.1 (2) | C8—C9—N1—C10 | 111.90 (18) |
| C2—C3—C4—Cl2 | 177.09 (12) | C8—C9—N1—C12 | −68.1 (2) |
| C3—C4—C5—C6 | 1.1 (3) | N1—C10—N2—C11 | 0.14 (18) |
| Cl2—C4—C5—C6 | −177.02 (13) | N1—C10—N2—C13 | −177.43 (15) |
| C4—C5—C6—C1 | −0.1 (3) | C12—C11—N2—C10 | −0.12 (19) |
| C2—C1—C6—C5 | −0.8 (2) | C12—C11—N2—C13 | 177.41 (16) |
| C7—C1—C6—C5 | 178.67 (15) | C1—C7—N3—C8 | −178.82 (14) |
| C2—C1—C7—N3 | 179.95 (16) | C9—C8—N3—C7 | 113.18 (17) |
| C6—C1—C7—N3 | 0.5 (2) |
| D—H···A | D—H | H···A | D···A | D—H···A |
| C7—H7···Cl1 | 0.95 | 2.69 | 3.0846 (17) | 106 |
| C12—H12···F2 | 0.95 | 2.48 | 3.239 (2) | 137 |
| C5—H5···F3 | 0.95 | 2.51 | 3.324 (2) | 143 |
| C11—H11···F6 | 0.95 | 2.46 | 3.275 (2) | 143 |
| C10—H10···F3i | 0.95 | 2.33 | 3.203 (2) | 152 |
| C10—H10···F5i | 0.95 | 2.54 | 3.373 (2) | 147 |
| C13—H13C···F5ii | 0.98 | 2.54 | 3.464 (2) | 158 |
| Symmetry codes: (i) x−1, y+1, z; (ii) −x+1, −y+1, −z. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| C7—H7···Cl1 | 0.95 | 2.69 | 3.0846 (17) | 106 |
| C12—H12···F2 | 0.95 | 2.48 | 3.239 (2) | 137 |
| C5—H5···F3 | 0.95 | 2.51 | 3.324 (2) | 143 |
| C11—H11···F6 | 0.95 | 2.46 | 3.275 (2) | 143 |
| C10—H10···F3i | 0.95 | 2.33 | 3.203 (2) | 152 |
| C10—H10···F5i | 0.95 | 2.54 | 3.373 (2) | 147 |
| C13—H13C···F5ii | 0.98 | 2.54 | 3.464 (2) | 158 |
| Symmetry codes: (i) x−1, y+1, z; (ii) −x+1, −y+1, −z. |
We are grateful to the National Natural Science Foundation of China (No. 20672046) and the Guangdong Natural Science Foundation (No. 8151063201000016) for financial support.
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Ionic liquids are attracting much interest in many fields of chemistry and industry, due to their potential as green solvents for a wide range of applications in synthesis, catalysis, electrochemistry, and liquid-liquid extractions (Wasserscheid et al., 2000; Singh, 2005; Noda, 2000). Schiff base compounds are one of most prevalent mixed-donor ligands in the field of coordination chemistry (Li et al., 2009). As part of our program aimed at developing a novel functionalized ionic liquid, we now report the crystal structure of a novel ionic liquid-supported Schiff base (I).
The asymmetric unit of the title compond, (I), a Schiff base derived ionic liquid, is comprised of an organic cation and a PF6 counter anion, Fig. 1. Bond lengths and angels are generally within normal ranges (Allen et al., 1987). The dihedral angle between the mean planes of the imidazole and benzene rings in the cation is 6.10°. The crystal structure exhibits weak C–H···Cl intramolecular and C–H···F intermolecular hydrogen bonding interactions as well as aromatic π–π stacking interactions between the imidazole and benzene rings of neighbouring cations [Cg1···Cg2 = 3.7203 (12)Å; 1-x, 1-y, 1-z, where Cg1 and Cg2 are centroids of the imidazole (N1/C10/N2/C11/C12) and benzene (C1–C6) rings, respectively, Fig. 2].