Acta Cryst. (2008). E64, m1620 [ doi:10.1107/S1600536808038932 ]
The crystal of the title compound, (C22H22N2)[ZnCl4], consists of 2,2'-(butane-1,4-diyl)diisoquinolinium organic cations and [ZnCl4]2- complex anions. The cation is located across a twofold axis and the ZnII atom of the anion is located on the other twofold axis. The centroid-centroid distance between parallel pyridine rings of neighboring molecules is 3.699 (3) Å, but the face-to-face separation of 3.601 (3) Å suggests there is no significant ![[pi]](/logos/entities/pi_rmgif.gif)
- stacking in the crystal structure.
A solution of 1,4-dibromine-butane (2.16 g, 0.01 mol) was added to a stirred solution of isoquinoline (2.58 g, 0.02 mol) in 1,4-dioxane (50 ml) at 373 K in a period of 5 h. After cooling to room temperature, the mixture was filtered. The residue was added to an aqueous solution (50 ml) of ZnCl2 (0.01 mol, 1.37 g). After stirring for 2 h, the solution was filtered. Colorless single crystals of the title compound were obtained from the filtrate after 5 weeks.
H atoms were placed in calculated positions with C—H = 0.93 (aromatic) or 0.97 Å (methylene), and refined in riding mode with Uiso(H) = 1.2Ueq(C). The highest peak and deepest hole in the final d-map are 0.35 Å from Cl2 atom and 0.42 Å from Zn1 atom, respectively.
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: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).
![[Figure 1]](./xu2462fig1thm.gif)
| Fig. 1. The molecular structure showing the atom-labeling scheme. Displacement ellipsoids are drawn at the 50% probability level [symmetry codes: (a) -x, y, 3/2-z; (b) -x, y, 1/2-z]. |
| (C22H22N2)[ZnCl4] | F(000) = 1064 |
| Mr = 521.61 | Dx = 1.563 Mg m−3 |
| Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -C 2yc | Cell parameters from 2184 reflections |
| a = 10.729 (3) Å | θ = 2.2–26.0° |
| b = 11.040 (3) Å | µ = 1.60 mm−1 |
| c = 18.955 (4) Å | T = 273 K |
| β = 99.179 (9)° | Prism, colorless |
| V = 2216.4 (10) Å3 | 0.23 × 0.19 × 0.17 mm |
| Z = 4 |
| Bruker SMART CCD area-detector diffractometer | 2172 independent reflections |
| Radiation source: fine-focus sealed tube | 1855 reflections with I > 2σ(I) |
| graphite | Rint = 0.032 |
| φ and ω scans | θmax = 26.0°, θmin = 2.2° |
| Absorption correction: multi-scan (SADABS; Bruker, 2005) | h = −13→13 |
| Tmin = 0.680, Tmax = 0.760 | k = −13→13 |
| 12088 measured reflections | l = −23→21 |
| 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)] = 0.058 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.206 | H-atom parameters constrained |
| S = 1.13 | w = 1/[σ2(Fo2) + (0.1169P)2 + 12.0521P] where P = (Fo2 + 2Fc2)/3 |
| 2172 reflections | (Δ/σ)max < 0.001 |
| 132 parameters | Δρmax = 1.28 e Å−3 |
| 0 restraints | Δρmin = −1.15 e Å−3 |
| (C22H22N2)[ZnCl4] | V = 2216.4 (10) Å3 |
| Mr = 521.61 | Z = 4 |
| Monoclinic, C2/c | Mo Kα radiation |
| a = 10.729 (3) Å | µ = 1.60 mm−1 |
| b = 11.040 (3) Å | T = 273 K |
| c = 18.955 (4) Å | 0.23 × 0.19 × 0.17 mm |
| β = 99.179 (9)° |
| Bruker SMART CCD area-detector diffractometer | 2172 independent reflections |
| Absorption correction: multi-scan (SADABS; Bruker, 2005) | 1855 reflections with I > 2σ(I) |
| Tmin = 0.680, Tmax = 0.760 | Rint = 0.032 |
| 12088 measured reflections | θmax = 26.0° |
| R[F2 > 2σ(F2)] = 0.058 | w = 1/[σ2(Fo2) + (0.1169P)2 + 12.0521P] where P = (Fo2 + 2Fc2)/3 |
| wR(F2) = 0.206 | Δρmax = 1.28 e Å−3 |
| S = 1.13 | Δρmin = −1.15 e Å−3 |
| 2172 reflections | Absolute structure: ? |
| 132 parameters | Flack parameter: ? |
| 0 restraints | Rogers parameter: ? |
| H-atom parameters constrained |
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 | ||
| Zn1 | 0.0000 | 0.15361 (8) | 0.2500 | 0.0412 (3) | |
| Cl2 | 0.12762 (10) | 0.03371 (11) | 0.19106 (6) | 0.0349 (4) | |
| Cl1 | 0.12438 (13) | 0.27560 (13) | 0.33123 (8) | 0.0483 (4) | |
| N1 | 0.4868 (4) | 0.1136 (4) | 0.3832 (2) | 0.0416 (10) | |
| C11 | 0.4355 (5) | 0.1981 (5) | 0.2617 (3) | 0.0449 (13) | |
| H11A | 0.4248 | 0.2744 | 0.2854 | 0.054* | |
| H11B | 0.3715 | 0.1945 | 0.2193 | 0.054* | |
| C3 | 0.6202 (6) | 0.1461 (5) | 0.5206 (3) | 0.0439 (13) | |
| C9 | 0.5975 (6) | 0.0584 (5) | 0.4013 (3) | 0.0442 (13) | |
| H9 | 0.6286 | 0.0098 | 0.3680 | 0.053* | |
| C10 | 0.4120 (6) | 0.0967 (6) | 0.3108 (3) | 0.0463 (13) | |
| H10A | 0.3228 | 0.0938 | 0.3143 | 0.056* | |
| H10B | 0.4347 | 0.0203 | 0.2910 | 0.056* | |
| C1 | 0.4382 (6) | 0.1876 (6) | 0.4311 (3) | 0.0528 (15) | |
| H1 | 0.3614 | 0.2265 | 0.4171 | 0.063* | |
| C8 | 0.6687 (5) | 0.0723 (5) | 0.4702 (3) | 0.0415 (12) | |
| C6 | 0.8489 (7) | 0.0222 (6) | 0.5569 (4) | 0.0583 (16) | |
| H6 | 0.9255 | −0.0177 | 0.5700 | 0.070* | |
| C7 | 0.7856 (6) | 0.0107 (6) | 0.4893 (3) | 0.0533 (15) | |
| H7 | 0.8182 | −0.0368 | 0.4560 | 0.064* | |
| C5 | 0.7995 (7) | 0.0947 (6) | 0.6080 (3) | 0.0581 (17) | |
| H5 | 0.8434 | 0.1003 | 0.6543 | 0.070* | |
| C4 | 0.6894 (7) | 0.1560 (6) | 0.5902 (3) | 0.0524 (15) | |
| H4 | 0.6594 | 0.2046 | 0.6239 | 0.063* | |
| C2 | 0.5011 (7) | 0.2039 (6) | 0.4980 (3) | 0.0542 (15) | |
| H2 | 0.4668 | 0.2532 | 0.5297 | 0.065* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Zn1 | 0.0383 (5) | 0.0406 (6) | 0.0448 (6) | 0.000 | 0.0074 (4) | 0.000 |
| Cl2 | 0.0276 (6) | 0.0410 (7) | 0.0363 (6) | 0.0026 (4) | 0.0056 (4) | −0.0100 (5) |
| Cl1 | 0.0393 (7) | 0.0457 (8) | 0.0587 (9) | −0.0063 (6) | 0.0043 (6) | −0.0239 (6) |
| N1 | 0.038 (2) | 0.046 (3) | 0.040 (2) | 0.000 (2) | 0.0034 (18) | 0.0025 (19) |
| C11 | 0.048 (3) | 0.045 (3) | 0.039 (3) | 0.005 (2) | −0.001 (2) | 0.002 (2) |
| C3 | 0.047 (3) | 0.044 (3) | 0.041 (3) | −0.005 (2) | 0.008 (2) | 0.000 (2) |
| C9 | 0.050 (3) | 0.044 (3) | 0.038 (3) | 0.001 (2) | 0.006 (2) | −0.001 (2) |
| C10 | 0.041 (3) | 0.053 (3) | 0.043 (3) | −0.006 (3) | 0.002 (2) | 0.000 (2) |
| C1 | 0.045 (3) | 0.061 (4) | 0.054 (4) | 0.006 (3) | 0.012 (3) | 0.003 (3) |
| C8 | 0.043 (3) | 0.041 (3) | 0.040 (3) | −0.003 (2) | 0.005 (2) | 0.002 (2) |
| C6 | 0.052 (4) | 0.058 (4) | 0.061 (4) | 0.005 (3) | −0.001 (3) | 0.006 (3) |
| C7 | 0.056 (4) | 0.056 (4) | 0.045 (3) | 0.009 (3) | 0.000 (3) | 0.001 (3) |
| C5 | 0.066 (4) | 0.062 (4) | 0.042 (3) | −0.014 (3) | −0.005 (3) | 0.008 (3) |
| C4 | 0.066 (4) | 0.053 (4) | 0.039 (3) | −0.006 (3) | 0.009 (3) | −0.002 (2) |
| C2 | 0.060 (4) | 0.060 (4) | 0.045 (3) | 0.009 (3) | 0.016 (3) | −0.005 (3) |
| Zn1—Cl1i | 2.3043 (14) | C9—H9 | 0.9300 |
| Zn1—Cl1 | 2.3043 (14) | C10—H10A | 0.9700 |
| Zn1—Cl2i | 2.3158 (12) | C10—H10B | 0.9700 |
| Zn1—Cl2 | 2.3158 (12) | C1—C2 | 1.350 (9) |
| N1—C9 | 1.330 (7) | C1—H1 | 0.9300 |
| N1—C1 | 1.384 (8) | C8—C7 | 1.423 (9) |
| N1—C10 | 1.488 (7) | C6—C7 | 1.357 (9) |
| C11—C10 | 1.502 (8) | C6—C5 | 1.423 (10) |
| C11—C11ii | 1.520 (12) | C6—H6 | 0.9300 |
| C11—H11A | 0.9700 | C7—H7 | 0.9300 |
| C11—H11B | 0.9700 | C5—C4 | 1.356 (10) |
| C3—C4 | 1.412 (9) | C5—H5 | 0.9300 |
| C3—C8 | 1.416 (8) | C4—H4 | 0.9300 |
| C3—C2 | 1.431 (9) | C2—H2 | 0.9300 |
| C9—C8 | 1.411 (8) | ||
| Cl1i—Zn1—Cl1 | 108.47 (9) | N1—C10—H10B | 109.4 |
| Cl1i—Zn1—Cl2i | 109.41 (5) | C11—C10—H10B | 109.4 |
| Cl1—Zn1—Cl2i | 109.62 (5) | H10A—C10—H10B | 108.0 |
| Cl1i—Zn1—Cl2 | 109.62 (5) | C2—C1—N1 | 120.7 (6) |
| Cl1—Zn1—Cl2 | 109.41 (5) | C2—C1—H1 | 119.7 |
| Cl2i—Zn1—Cl2 | 110.28 (7) | N1—C1—H1 | 119.7 |
| C9—N1—C1 | 121.0 (5) | C9—C8—C3 | 118.9 (5) |
| C9—N1—C10 | 120.6 (5) | C9—C8—C7 | 120.6 (5) |
| C1—N1—C10 | 118.4 (5) | C3—C8—C7 | 120.4 (5) |
| C10—C11—C11ii | 115.5 (4) | C7—C6—C5 | 120.7 (6) |
| C10—C11—H11A | 108.4 | C7—C6—H6 | 119.7 |
| C11ii—C11—H11A | 108.4 | C5—C6—H6 | 119.7 |
| C10—C11—H11B | 108.4 | C6—C7—C8 | 119.0 (6) |
| C11ii—C11—H11B | 108.4 | C6—C7—H7 | 120.5 |
| H11A—C11—H11B | 107.5 | C8—C7—H7 | 120.5 |
| C4—C3—C8 | 118.7 (6) | C4—C5—C6 | 121.1 (6) |
| C4—C3—C2 | 123.8 (6) | C4—C5—H5 | 119.5 |
| C8—C3—C2 | 117.5 (5) | C6—C5—H5 | 119.5 |
| N1—C9—C8 | 121.2 (5) | C5—C4—C3 | 120.1 (6) |
| N1—C9—H9 | 119.4 | C5—C4—H4 | 120.0 |
| C8—C9—H9 | 119.4 | C3—C4—H4 | 120.0 |
| N1—C10—C11 | 111.1 (5) | C1—C2—C3 | 120.7 (6) |
| N1—C10—H10A | 109.4 | C1—C2—H2 | 119.7 |
| C11—C10—H10A | 109.4 | C3—C2—H2 | 119.7 |
| C1—N1—C9—C8 | 0.7 (9) | C2—C3—C8—C7 | −179.1 (6) |
| C10—N1—C9—C8 | −179.1 (5) | C5—C6—C7—C8 | 0.0 (10) |
| C9—N1—C10—C11 | −96.2 (6) | C9—C8—C7—C6 | −177.3 (6) |
| C1—N1—C10—C11 | 83.9 (6) | C3—C8—C7—C6 | 1.0 (9) |
| C11ii—C11—C10—N1 | 71.4 (7) | C7—C6—C5—C4 | −1.3 (10) |
| C9—N1—C1—C2 | −1.2 (9) | C6—C5—C4—C3 | 1.6 (10) |
| C10—N1—C1—C2 | 178.6 (6) | C8—C3—C4—C5 | −0.5 (9) |
| N1—C9—C8—C3 | 0.3 (8) | C2—C3—C4—C5 | 177.7 (6) |
| N1—C9—C8—C7 | 178.6 (6) | N1—C1—C2—C3 | 0.7 (10) |
| C4—C3—C8—C9 | 177.6 (5) | C4—C3—C2—C1 | −178.0 (6) |
| C2—C3—C8—C9 | −0.7 (8) | C8—C3—C2—C1 | 0.2 (10) |
| C4—C3—C8—C7 | −0.8 (9) |
| Symmetry codes: (i) −x, y, −z+1/2; (ii) −x+1, y, −z+1/2. |
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As part of our ongoing investigation on quinoline compounds, we present here the crystal structure of the compound with multiple functional groups, which can develop strong intermolecular interactions with cucurbit[n]urils (CB[n]) (Freeman et al., 1981; Day & Arnold, 2000; Day et al., 2002; Kim et al., 2000).
The crystal structure of the title compound (Fig. 1) consists of organic cations and anionic (ZnCl4)2- complexes. The (ZnCl4)2- anion assumes a distorted tetrahedron coordination geometry with Zn–Cl bond distances of 2.3043 (14) Å and 2.3158 (12) Å. The centroids distance between parallel pyridine rings of neighboring molecules is 3.699 (3) Å, but the face-to-face separation of 3.601 (3) Å suggests no significant π-π stacking in the crystal structure (Pan & Xu, 2004).