supplementary materials
1-(4-Chlorobenzylideneamino)pyridinum iodide
In the title compound, C12H10ClN2+·I-, the aromatic rings are oriented at a dihedral angle of 54.55 (3)°. In the crystal structure, intermolecular C-H
I and C-HCl hydrogen bonds link the molecules.
For the preparation of the title compound, 1-aminopyridinium iodide (22.2 g,
0.10 mol) was dissolved in ethanol (20 ml), 4-methylbenzaldehyde (12.4 g,
0.1 mol) was added with stirring, and then the mixture was heated at reflux
for 5 h. Upon cooling to room temperature, a precipitate formed, which was
collected by filtration and washed with cold ethanol (2 X 10 ml) to obtain a
yellow solid (yield; 24.0 g, 70%). Crystals suitable for X-ray analysis were
obtained by slow evaporation of an ethanol solution.
H atoms were positioned geometrically, with C-H = 0.93 Å for aromatic and
methine H 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: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).
1-(4-Chlorobenzylideneamino)pyridinum iodide
top
Crystal data top
| C12H10ClN2+·I− | Z = 2 |
| Mr = 344.57 | F(000) = 332 |
| Triclinic, P1 | Dx = 1.814 Mg m−3 |
| Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
| a = 6.5105 (14) Å | Cell parameters from 25 reflections |
| b = 7.1748 (15) Å | θ = 2.1–25.3° |
| c = 14.223 (3) Å | µ = 2.72 mm−1 |
| α = 76.893 (3)° | T = 291 K |
| β = 79.183 (3)° | Block, yellow |
| γ = 80.753 (3)° | 0.10 × 0.10 × 0.08 mm |
| V = 630.7 (2) Å3 | |
Data collection top
Enraf–Nonius CAD-4
diffractometer | 1892 reflections with I > 2σ(I) |
| Radiation source: fine-focus sealed tube | Rint = 0.063 |
| graphite | θmax = 25.0°, θmin = 2.9° |
| ω/2θ scans | h = −7→7 |
Absorption correction: ψ scan
(North et al., 1968) | k = −8→8 |
| Tmin = 0.772, Tmax = 0.812 | l = −15→16 |
| 3220 measured reflections | 3 standard reflections every 120 min |
| 2205 independent reflections | intensity decay: none |
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)] = 0.027 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.093 | H-atom parameters constrained |
| S = 1.05 | w = 1/[σ2(Fo2) + (0.0479P)2]
where P = (Fo2 + 2Fc2)/3 |
| 2205 reflections | (Δ/σ)max < 0.001 |
| 145 parameters | Δρmax = 0.53 e Å−3 |
| 0 restraints | Δρmin = −0.63 e Å−3 |
Crystal data top
| C12H10ClN2+·I− | γ = 80.753 (3)° |
| Mr = 344.57 | V = 630.7 (2) Å3 |
| Triclinic, P1 | Z = 2 |
| a = 6.5105 (14) Å | Mo Kα radiation |
| b = 7.1748 (15) Å | µ = 2.72 mm−1 |
| c = 14.223 (3) Å | T = 291 K |
| α = 76.893 (3)° | 0.10 × 0.10 × 0.08 mm |
| β = 79.183 (3)° | |
Data collection top
Enraf–Nonius CAD-4
diffractometer | 1892 reflections with I > 2σ(I) |
Absorption correction: ψ scan
(North et al., 1968) | Rint = 0.063 |
| Tmin = 0.772, Tmax = 0.812 | θmax = 25.0° |
| 3220 measured reflections | 3 standard reflections every 120 min |
| 2205 independent reflections | intensity decay: none |
Refinement top
| R[F2 > 2σ(F2)] = 0.027 | H-atom parameters constrained |
| wR(F2) = 0.093 | Δρmax = 0.53 e Å−3 |
| S = 1.05 | Δρmin = −0.63 e Å−3 |
| 2205 reflections | Absolute structure: ? |
| 145 parameters | Flack parameter: ? |
| 0 restraints | Rogers parameter: ? |
Special details top
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top| | x | y | z | Uiso*/Ueq | |
| I1 | 0.91966 (5) | 0.25912 (5) | 0.16564 (2) | 0.05410 (17) | |
| Cl1 | 0.1793 (2) | 0.4285 (2) | 0.64323 (10) | 0.0562 (3) | |
| N1 | 0.4087 (6) | −0.1676 (5) | 0.2056 (3) | 0.0410 (9) | |
| N2 | 0.3499 (6) | −0.1179 (6) | 0.3000 (3) | 0.0434 (9) | |
| C1 | 0.6038 (8) | −0.1437 (7) | 0.1537 (4) | 0.0495 (12) | |
| H1 | 0.7003 | −0.0912 | 0.1775 | 0.059* | |
| C2 | 0.6541 (10) | −0.1996 (7) | 0.0648 (4) | 0.0608 (15) | |
| H2 | 0.7863 | −0.1852 | 0.0274 | 0.073* | |
| C3 | 0.5076 (10) | −0.2770 (7) | 0.0313 (4) | 0.0585 (14) | |
| H3 | 0.5404 | −0.3131 | −0.0291 | 0.070* | |
| C4 | 0.3107 (11) | −0.3012 (8) | 0.0878 (4) | 0.0654 (16) | |
| H4 | 0.2111 | −0.3533 | 0.0658 | 0.079* | |
| C5 | 0.2669 (9) | −0.2469 (7) | 0.1763 (4) | 0.0562 (13) | |
| H5 | 0.1380 | −0.2654 | 0.2160 | 0.067* | |
| C6 | 0.3740 (8) | 0.0561 (7) | 0.2976 (3) | 0.0451 (11) | |
| H6 | 0.4240 | 0.1326 | 0.2382 | 0.054* | |
| C7 | 0.3254 (7) | 0.1391 (7) | 0.3855 (3) | 0.0415 (11) | |
| C8 | 0.2488 (7) | 0.0346 (7) | 0.4776 (3) | 0.0442 (11) | |
| H8 | 0.2289 | −0.0937 | 0.4851 | 0.053* | |
| C9 | 0.2026 (8) | 0.1216 (7) | 0.5574 (3) | 0.0474 (12) | |
| H9 | 0.1510 | 0.0536 | 0.6189 | 0.057* | |
| C10 | 0.2355 (7) | 0.3145 (7) | 0.5436 (3) | 0.0424 (11) | |
| C11 | 0.3049 (8) | 0.4181 (7) | 0.4539 (3) | 0.0479 (12) | |
| H11 | 0.3202 | 0.5476 | 0.4461 | 0.058* | |
| C12 | 0.3526 (8) | 0.3297 (7) | 0.3745 (3) | 0.0460 (11) | |
| H12 | 0.4033 | 0.3992 | 0.3132 | 0.055* | |
Atomic displacement parameters (Å2) top| | U11 | U22 | U33 | U12 | U13 | U23 |
| I1 | 0.0580 (3) | 0.0587 (3) | 0.0457 (2) | −0.01153 (17) | −0.00263 (16) | −0.01233 (16) |
| Cl1 | 0.0519 (8) | 0.0723 (9) | 0.0497 (7) | −0.0091 (6) | −0.0010 (6) | −0.0280 (6) |
| N1 | 0.041 (2) | 0.043 (2) | 0.039 (2) | −0.0075 (18) | −0.0030 (18) | −0.0090 (17) |
| N2 | 0.045 (2) | 0.048 (2) | 0.038 (2) | −0.0064 (18) | −0.0026 (17) | −0.0132 (17) |
| C1 | 0.055 (3) | 0.048 (3) | 0.043 (3) | −0.004 (2) | −0.004 (2) | −0.009 (2) |
| C2 | 0.076 (4) | 0.050 (3) | 0.046 (3) | 0.001 (3) | 0.009 (3) | −0.010 (2) |
| C3 | 0.083 (4) | 0.047 (3) | 0.044 (3) | −0.009 (3) | 0.000 (3) | −0.016 (2) |
| C4 | 0.094 (5) | 0.050 (3) | 0.061 (4) | −0.006 (3) | −0.023 (3) | −0.021 (3) |
| C5 | 0.060 (4) | 0.055 (3) | 0.055 (3) | −0.009 (3) | −0.008 (3) | −0.014 (3) |
| C6 | 0.050 (3) | 0.049 (3) | 0.036 (3) | 0.001 (2) | −0.008 (2) | −0.010 (2) |
| C7 | 0.037 (3) | 0.050 (3) | 0.038 (3) | 0.003 (2) | −0.008 (2) | −0.014 (2) |
| C8 | 0.041 (3) | 0.046 (3) | 0.043 (3) | −0.004 (2) | −0.003 (2) | −0.009 (2) |
| C9 | 0.047 (3) | 0.056 (3) | 0.036 (3) | −0.007 (2) | 0.000 (2) | −0.008 (2) |
| C10 | 0.034 (3) | 0.056 (3) | 0.041 (3) | −0.006 (2) | −0.006 (2) | −0.017 (2) |
| C11 | 0.055 (3) | 0.044 (3) | 0.046 (3) | −0.008 (2) | −0.009 (2) | −0.009 (2) |
| C12 | 0.052 (3) | 0.047 (3) | 0.037 (3) | −0.010 (2) | −0.006 (2) | −0.003 (2) |
Geometric parameters (Å, °) top
| Cl1—C10 | 1.746 (5) | C5—H5 | 0.9300 |
| N1—C5 | 1.331 (7) | C6—C7 | 1.465 (6) |
| N1—C1 | 1.359 (6) | C6—H6 | 0.9300 |
| N1—N2 | 1.434 (5) | C7—C12 | 1.377 (6) |
| N2—C6 | 1.275 (6) | C7—C8 | 1.399 (6) |
| C1—C2 | 1.379 (7) | C8—C9 | 1.378 (6) |
| C1—H1 | 0.9300 | C8—H8 | 0.9300 |
| C2—C3 | 1.380 (8) | C9—C10 | 1.399 (7) |
| C2—H2 | 0.9300 | C9—H9 | 0.9300 |
| C3—C4 | 1.393 (9) | C10—C11 | 1.358 (7) |
| C3—H3 | 0.9300 | C11—C12 | 1.380 (6) |
| C4—C5 | 1.367 (7) | C11—H11 | 0.9300 |
| C4—H4 | 0.9300 | C12—H12 | 0.9300 |
| | | |
| C5—N1—C1 | 123.4 (4) | N2—C6—H6 | 119.0 |
| C5—N1—N2 | 116.0 (4) | C7—C6—H6 | 119.0 |
| C1—N1—N2 | 120.4 (4) | C12—C7—C8 | 119.8 (4) |
| C6—N2—N1 | 112.2 (4) | C12—C7—C6 | 117.4 (4) |
| N1—C1—C2 | 118.0 (5) | C8—C7—C6 | 122.8 (4) |
| N1—C1—H1 | 121.0 | C9—C8—C7 | 120.1 (4) |
| C2—C1—H1 | 121.0 | C9—C8—H8 | 119.9 |
| C1—C2—C3 | 119.7 (5) | C7—C8—H8 | 119.9 |
| C1—C2—H2 | 120.1 | C8—C9—C10 | 118.4 (4) |
| C3—C2—H2 | 120.1 | C8—C9—H9 | 120.8 |
| C2—C3—C4 | 120.2 (5) | C10—C9—H9 | 120.8 |
| C2—C3—H3 | 119.9 | C11—C10—C9 | 121.8 (4) |
| C4—C3—H3 | 119.9 | C11—C10—Cl1 | 118.7 (4) |
| C5—C4—C3 | 118.6 (5) | C9—C10—Cl1 | 119.5 (4) |
| C5—C4—H4 | 120.7 | C10—C11—C12 | 119.5 (4) |
| C3—C4—H4 | 120.7 | C10—C11—H11 | 120.2 |
| N1—C5—C4 | 120.0 (5) | C12—C11—H11 | 120.2 |
| N1—C5—H5 | 120.0 | C7—C12—C11 | 120.4 (4) |
| C4—C5—H5 | 120.0 | C7—C12—H12 | 119.8 |
| N2—C6—C7 | 122.0 (4) | C11—C12—H12 | 119.8 |
Hydrogen-bond geometry (Å, °) top
| D—H···A | D—H | H···A | D···A | D—H···A |
| C1—H1···I1 | 0.93 | 3.04 | 3.857 (5) | 147 |
| C5—H5···Cl1i | 0.93 | 2.79 | 3.691 (6) | 162 |
| Symmetry codes: (i) −x, −y, −z+1. |
Table 1
Hydrogen-bond geometry (Å, °) top
| D—H···A | D—H | H···A | D···A | D—H···A |
| C1—H1···I1 | 0.93 | 3.04 | 3.857 (5) | 147 |
| C5—H5···Cl1i | 0.93 | 2.79 | 3.691 (6) | 162 |
| Symmetry codes: (i) −x, −y, −z+1. |
The authors thank the Center of Testing and Analysis, Nanjing University, for
support.
Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19.
Enraf–Nonius (1989). CAD-4 Software. Enraf–Nonius, Delft. The Netherlands.
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.
Harms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany.
North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359.
Okamoto, T., Hirobe, M. & Sato, R. (1967). Yakugaku Zasshi, 87, 994–996.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
![[Figure 1]](./hk2600fig1thm.gif)
![[Figure 2]](./hk2600fig2thm.gif)
Some derivatives of 1-aminopyidium iodide are important chemical materials. We report herein the crystal structure of the title compound.
In the molecule of the title compound (Fig. 1), the bond lengths (Allen et al., 1987) and angles are within normal ranges. Rings A (N1/C1-C5) and B (C7-C12) are, of course, planar, and they are oriented at a dihedral angle of 54.55 (3)°.
In the crystal structure, intramolecular C-H···I and intermolecular C-H···Cl hydrogen bonds (Table 1) link the molecules (Fig. 2), in which they may be effective in the stabilization of the structure. The π-π contacts between the pyridine rings and the benzene rings, Cg1—Cg1i and Cg2—Cg2ii [symmetry codes: (i) 1 - x, -y, -z; (ii) 1 - x, -y, 1 - z, where Cg1 and Cg2 are centroids of the rings A (N1/C1-C5) and B (C7-C12) , respectively] may further stabilize the structure, with centroid-centroid distances of 4.130 (3) Å and 4.056 (3) Å.