1-(4-Chloro­benzyl­ideneamino)pyridinum iodide

Cui, Y.-T.; Wang, J.-Q.; Ji, C.-X.; Wang, H.-B.; Cheng, G.

doi:10.1107/S1600536808043729

organic compounds

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ISSN: 2056-9890

Volume 65| Part 2| February 2009| Page o228

doi:10.1107/S1600536808043729

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1-(4-Chlorobenzylideneamino)pyridinum iodide

Yong-Tao Cui,^a Jian-Qiang Wang,^a Chun-Xiang Ji,^a Hai-Bo Wang ^a and Guo Cheng ^a ^*

^aCollege of Science, Nanjing University of Technolgy, Xinmofan Road No. 5 Nanjing, Nanjing 210009, People's Republic of China
^*Correspondence e-mail: guocheng@njut.edu.cn

(Received 17 December 2008; accepted 23 December 2008; online 8 January 2009)

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—H⋯Cl hydrogen bonds link the molecules.

Related literature

For background, see: Okamoto et al. (1967 ). For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₁₂H₁₀ClN₂⁺·I⁻
M_r = 344.57
Triclinic, $[P \overline 1]$
a = 6.5105 (14) Å
b = 7.1748 (15) Å
c = 14.223 (3) Å
α = 76.893 (3)°
β = 79.183 (3)°
γ = 80.753 (3)°
V = 630.7 (2) Å³
Z = 2
Mo Kα radiation
μ = 2.72 mm⁻¹
T = 291 (2) K
0.10 × 0.10 × 0.08 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.772, T_max = 0.812
3220 measured reflections
2205 independent reflections
1892 reflections with I > 2σ(I)
R_int = 0.063
3 standard reflections frequency: 120 min intensity decay: none

Refinement

R[F² > 2σ(F²)] = 0.027
wR(F²) = 0.093
S = 1.05
2205 reflections
145 parameters
H-atom parameters constrained
Δρ_max = 0.53 e Å⁻³
Δρ_min = −0.63 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

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 code: (i) -x, -y, -z+1.

Data collection: CAD-4 Software (Enraf–Nonius, 1989 ); cell refinement: CAD-4 Software; 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.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808043729/hk2600sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808043729/hk2600Isup2.hkl

checkCIF report

Comment top

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.

Related literature top

For background, see: Okamoto et al. (1967). For bond-length data, see: Allen et al. (1987).

Experimental top

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.

Computing details top

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).

Figures top

	Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. A partial packing diagram of the title compound. Hydrogen bonds are shown as dashed lines.

1-(4-Chlorobenzylideneamino)pyridinum iodide top

Crystal data top

C₁₂H₁₀ClN₂⁺·I⁻	Z = 2
M_r = 344.57	F(000) = 332
Triclinic, P1	D_x = 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	R_int = 0.063
Graphite monochromator	θ_max = 25.0°, θ_min = 2.9°
ω/2θ scans	h = −7→7
Absorption correction: ψ scan (North et al., 1968)	k = −8→8
T_min = 0.772, T_max = 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(F_o²) + (0.0479P)²] where P = (F_o² + 2F_c²)/3
2205 reflections	(Δ/σ)_max < 0.001
145 parameters	Δρ_max = 0.53 e Å⁻³
0 restraints	Δρ_min = −0.63 e Å⁻³

Crystal data top

C₁₂H₁₀ClN₂⁺·I⁻	γ = 80.753 (3)°
M_r = 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)	R_int = 0.063
T_min = 0.772, T_max = 0.812	3 standard reflections every 120 min
3220 measured reflections	intensity decay: none
2205 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.027	0 restraints
wR(F²) = 0.093	H-atom parameters constrained
S = 1.05	Δρ_max = 0.53 e Å⁻³
2205 reflections	Δρ_min = −0.63 e Å⁻³
145 parameters

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	U_iso*/U_eq
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, º) 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, º) 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 code: (i) −x, −y, −z+1.

Experimental details

Crystal data
Chemical formula	C₁₂H₁₀ClN₂⁺·I⁻
M_r	344.57
Crystal system, space group	Triclinic, P1
Temperature (K)	291
a, b, c (Å)	6.5105 (14), 7.1748 (15), 14.223 (3)
α, β, γ (°)	76.893 (3), 79.183 (3), 80.753 (3)
V (Å³)	630.7 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	2.72
Crystal size (mm)	0.10 × 0.10 × 0.08

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.772, 0.812
No. of measured, independent and observed [I > 2σ(I)] reflections	3220, 2205, 1892
R_int	0.063
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.027, 0.093, 1.05
No. of reflections	2205
No. of parameters	145
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.53, −0.63

Computer programs: CAD-4 Software (Enraf–Nonius, 1989), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···I1	0.93	3.04	3.857 (5)	147.00
C5—H5···Cl1ⁱ	0.93	2.79	3.691 (6)	162.00

Symmetry code: (i) −x, −y, −z+1.

Acknowledgements

The authors thank the Center of Testing and Analysis, Nanjing University, for support.

References

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. CrossRef Web of Science Google Scholar
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