1-(4-Methyl­benzyl­ideneamino)pyridinium iodide

Cui, Y.-T.; Ji, C.-X.; You, W.; Sun, J.-S.; Guo, C.

doi:10.1107/S1600536808021569

organic compounds

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ISSN: 2056-9890

Volume 64| Part 8| August 2008| Page o1506

doi:10.1107/S1600536808021569

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1-(4-Methylbenzylideneamino)pyridinium iodide

Yong-Tao Cui,^a Chun-Xiang Ji,^a Wei You,^a Jia-Sen Sun ^a and Cheng Guo ^a ^*

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

(Received 11 July 2008; accepted 11 July 2008; online 16 July 2008)

The title compound, C₁₃H₁₃N₂⁺·I⁻, is a derivative of 1-aminopyridinium iodide. The pyridine and benzene rings are oriented at a dihedral angle of 45.78 (3)°. In the crystal structure, weak intermolecular C—H⋯I hydrogen bonds link the molecules.

Related literature

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

Experimental

Crystal data

C₁₃H₁₃N₂⁺·I⁻
M_r = 324.15
Orthorhombic, P 2₁ 2₁ 2₁
a = 7.1690 (14) Å
b = 12.399 (3) Å
c = 15.026 (3) Å
V = 1335.6 (5) Å³
Z = 4
Mo Kα radiation
μ = 2.37 mm⁻¹
T = 291 (2) K
0.30 × 0.10 × 0.10 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.536, T_max = 0.797
1408 measured reflections
1408 independent reflections
1015 reflections with I > 2σ(I)
3 standard reflections frequency: 120 min intensity decay: none

Refinement

R[F² > 2σ(F²)] = 0.048
wR(F²) = 0.125
S = 1.08
1408 reflections
146 parameters
H-atom parameters constrained
Δρ_max = 1.10 e Å⁻³
Δρ_min = −0.54 e Å⁻³
Absolute structure: Flack (1983 ), with no Friedel pairs
Flack parameter: 0.05 (10)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C9—H9⋯Iⁱ	0.93	3.06	3.795 (12)	138
C12—H12⋯Iⁱⁱ	0.93	3.03	3.929 (13)	162
Symmetry codes: (i) $[-x+1, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) $[x-{\script{1\over 2}}, -y+{\script{3\over 2}}, -z+1]$ .

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: SHELXTL (Sheldrick, 2008).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808021569/hk2492sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808021569/hk2492Isup2.hkl

checkCIF report

Comment top

Some derivatives of 1-aminopyidinium iodide is 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 (C2-C7) and B (N1/C9-C13) are, of course, planar and they are oriented at a dihedral angle of A/B = 45.78 (3)°.

In the crystal structure, weak intermolecular C-H···I hydrogen bonds (Table 1) link the molecules (Fig. 2), in which they may be effective in the stabilization of the structure.

Related literature top

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 (32.4 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; 38 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: SHELXTL (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 packing diagram of the title molecule. Hydrogen bonds are shown as dashed lines.

1-(4-Methylbenzylideneamino)pyridinium iodide top

Crystal data top

C₁₃H₁₃N₂⁺·I⁻	F(000) = 632
M_r = 324.15	D_x = 1.612 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 25 reflections
a = 7.1690 (14) Å	θ = 2.1–25.3°
b = 12.399 (3) Å	µ = 2.37 mm⁻¹
c = 15.026 (3) Å	T = 291 K
V = 1335.6 (5) Å³	Block, yellow
Z = 4	0.30 × 0.10 × 0.10 mm

Data collection top

Enraf–Nonius CAD-4 diffractometer	1015 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.000
Graphite monochromator	θ_max = 25.3°, θ_min = 2.1°
ω/2θ scans	h = 0→8
Absorption correction: ψ scan (North et al., 1968)	k = 0→14
T_min = 0.536, T_max = 0.797	l = 0→18
1408 measured reflections	3 standard reflections every 120 min
1408 independent reflections	intensity decay: none

Refinement top

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)] = 0.048	H-atom parameters constrained
wR(F²) = 0.125	w = 1/[σ²(F_o²) + (0.0599P)² + 0.581P] where P = (F_o² + 2F_c²)/3
S = 1.08	(Δ/σ)_max < 0.001
1408 reflections	Δρ_max = 1.10 e Å⁻³
146 parameters	Δρ_min = −0.54 e Å⁻³
0 restraints	Absolute structure: Flack (1983), with no Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.05 (10)

Crystal data top

C₁₃H₁₃N₂⁺·I⁻	V = 1335.6 (5) Å³
M_r = 324.15	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 7.1690 (14) Å	µ = 2.37 mm⁻¹
b = 12.399 (3) Å	T = 291 K
c = 15.026 (3) Å	0.30 × 0.10 × 0.10 mm

Data collection top

Enraf–Nonius CAD-4 diffractometer	1015 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.000
T_min = 0.536, T_max = 0.797	3 standard reflections every 120 min
1408 measured reflections	intensity decay: none
1408 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.048	H-atom parameters constrained
wR(F²) = 0.125	Δρ_max = 1.10 e Å⁻³
S = 1.08	Δρ_min = −0.54 e Å⁻³
1408 reflections	Absolute structure: Flack (1983), with no Friedel pairs
146 parameters	Absolute structure parameter: 0.05 (10)
0 restraints

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 > 2sigma(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
I	0.63765 (9)	0.75120 (8)	0.67606 (4)	0.0632 (3)
N1	0.1554 (13)	0.6174 (7)	0.7189 (6)	0.049 (2)
N2	0.1485 (13)	0.6612 (8)	0.8065 (6)	0.051 (2)
C1	0.241 (2)	1.0008 (11)	1.1391 (8)	0.068 (4)
H1A	0.3685	1.0169	1.1541	0.102*
H1B	0.1854	0.9596	1.1862	0.102*
H1C	0.1735	1.0669	1.1313	0.102*
C2	0.2358 (15)	0.9358 (10)	1.0529 (7)	0.053 (3)
C3	0.1465 (17)	0.8349 (9)	1.0519 (7)	0.055 (3)
H3	0.0964	0.8069	1.1041	0.065*
C4	0.1329 (14)	0.7771 (8)	0.9731 (7)	0.048 (3)
H4	0.0746	0.7101	0.9727	0.058*
C5	0.2057 (14)	0.8187 (9)	0.8955 (7)	0.044 (3)
C6	0.2865 (17)	0.9199 (8)	0.8960 (8)	0.055 (3)
H6	0.3312	0.9490	0.8431	0.066*
C7	0.3023 (16)	0.9792 (10)	0.9746 (8)	0.059 (3)
H7	0.3570	1.0472	0.9742	0.071*
C8	0.2037 (13)	0.7578 (10)	0.8115 (6)	0.051 (3)
H8	0.2447	0.7918	0.7599	0.062*
C9	0.2109 (17)	0.5139 (9)	0.7163 (9)	0.061 (3)
H9	0.2361	0.4769	0.7688	0.073*
C10	0.230 (2)	0.4624 (11)	0.6341 (12)	0.081 (5)
H10	0.2715	0.3914	0.6305	0.097*
C11	0.1874 (17)	0.5193 (13)	0.5595 (9)	0.072 (4)
H11	0.1953	0.4859	0.5042	0.087*
C12	0.1332 (19)	0.6237 (12)	0.5642 (8)	0.070 (4)
H12	0.1104	0.6627	0.5125	0.084*
C13	0.1126 (18)	0.6708 (11)	0.6443 (8)	0.065 (3)
H13	0.0681	0.7411	0.6478	0.078*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.078 (10)	0.073 (8)	0.054 (7)	0.006 (8)	−0.006 (8)	−0.019 (7)
C2	0.046 (7)	0.058 (8)	0.055 (7)	0.013 (6)	−0.012 (6)	0.001 (6)
C3	0.068 (8)	0.046 (6)	0.050 (7)	0.009 (7)	0.016 (6)	0.011 (5)
C4	0.052 (6)	0.044 (7)	0.048 (5)	0.002 (5)	−0.007 (5)	0.001 (5)
C5	0.033 (5)	0.060 (7)	0.038 (6)	0.007 (5)	0.006 (5)	0.006 (5)
C6	0.059 (7)	0.043 (6)	0.062 (7)	−0.007 (6)	0.020 (6)	0.001 (6)
C7	0.054 (7)	0.064 (8)	0.059 (7)	0.007 (6)	0.002 (7)	0.000 (7)
C8	0.039 (4)	0.073 (8)	0.042 (5)	0.013 (8)	0.001 (4)	0.011 (8)
C9	0.068 (8)	0.055 (8)	0.061 (7)	−0.011 (7)	−0.013 (7)	0.007 (6)
C10	0.070 (10)	0.064 (9)	0.108 (12)	−0.016 (9)	0.011 (10)	−0.026 (10)
C11	0.046 (8)	0.117 (13)	0.053 (8)	−0.017 (9)	0.015 (6)	−0.025 (9)
C12	0.072 (9)	0.094 (11)	0.044 (7)	−0.016 (9)	−0.018 (7)	0.001 (7)
C13	0.064 (8)	0.075 (8)	0.054 (7)	0.010 (8)	0.007 (7)	0.009 (7)
I	0.0631 (5)	0.0721 (5)	0.0544 (4)	0.0063 (8)	0.0064 (4)	−0.0020 (6)
N1	0.044 (5)	0.050 (5)	0.053 (5)	0.000 (5)	0.006 (5)	0.001 (5)
N2	0.049 (5)	0.054 (5)	0.049 (5)	−0.012 (5)	0.021 (5)	−0.005 (4)

Geometric parameters (Å, º) top

C1—C2	1.526 (15)	C8—N2	1.264 (13)
C1—H1A	0.9600	C8—H8	0.9300
C1—H1B	0.9600	C9—N1	1.344 (13)
C1—H1C	0.9600	C9—C10	1.398 (17)
C2—C7	1.379 (15)	C9—H9	0.9300
C2—C3	1.405 (16)	C10—C11	1.360 (19)
C3—C4	1.387 (15)	C10—H10	0.9300
C3—H3	0.9300	C11—C12	1.353 (17)
C4—C5	1.379 (13)	C11—H11	0.9300
C4—H4	0.9300	C12—C13	1.345 (16)
C5—C6	1.382 (14)	C12—H12	0.9300
C5—C8	1.471 (13)	C13—N1	1.338 (14)
C6—C7	1.396 (15)	C13—H13	0.9300
C6—H6	0.9300	N1—N2	1.425 (11)
C7—H7	0.9300

C2—C1—H1A	109.5	C6—C7—H7	120.4
C2—C1—H1B	109.5	N2—C8—C5	122.7 (9)
H1A—C1—H1B	109.5	N2—C8—H8	118.6
C2—C1—H1C	109.5	C5—C8—H8	118.6
H1A—C1—H1C	109.5	N1—C9—C10	119.4 (12)
H1B—C1—H1C	109.5	N1—C9—H9	120.3
C7—C2—C3	119.7 (11)	C10—C9—H9	120.3
C7—C2—C1	120.6 (12)	C11—C10—C9	118.0 (12)
C3—C2—C1	119.4 (12)	C11—C10—H10	121.0
C4—C3—C2	120.1 (10)	C9—C10—H10	121.0
C4—C3—H3	120.0	C12—C11—C10	121.2 (13)
C2—C3—H3	120.0	C12—C11—H11	119.4
C5—C4—C3	120.2 (10)	C10—C11—H11	119.4
C5—C4—H4	119.9	C13—C12—C11	119.6 (13)
C3—C4—H4	119.9	C13—C12—H12	120.2
C4—C5—C6	119.6 (10)	C11—C12—H12	120.2
C4—C5—C8	122.0 (10)	N1—C13—C12	120.6 (12)
C6—C5—C8	118.4 (10)	N1—C13—H13	119.7
C5—C6—C7	121.1 (11)	C12—C13—H13	119.7
C5—C6—H6	119.4	C13—N1—C9	121.1 (11)
C7—C6—H6	119.4	C13—N1—N2	125.3 (9)
C2—C7—C6	119.2 (11)	C9—N1—N2	113.6 (10)
C2—C7—H7	120.4	C8—N2—N1	113.9 (9)

C7—C2—C3—C4	2.9 (16)	N1—C9—C10—C11	−2 (2)
C1—C2—C3—C4	177.1 (11)	C9—C10—C11—C12	2 (2)
C2—C3—C4—C5	−0.5 (17)	C10—C11—C12—C13	−3 (2)
C3—C4—C5—C6	−2.2 (16)	C11—C12—C13—N1	4 (2)
C3—C4—C5—C8	176.6 (10)	C12—C13—N1—C9	−3.4 (19)
C4—C5—C6—C7	2.5 (17)	C12—C13—N1—N2	176.5 (11)
C8—C5—C6—C7	−176.3 (10)	C10—C9—N1—C13	2.3 (18)
C3—C2—C7—C6	−2.6 (17)	C10—C9—N1—N2	−177.6 (11)
C1—C2—C7—C6	−176.7 (12)	C5—C8—N2—N1	179.2 (9)
C5—C6—C7—C2	0.0 (18)	C13—N1—N2—C8	−38.8 (15)
C4—C5—C8—N2	−5.4 (16)	C9—N1—N2—C8	141.1 (10)
C6—C5—C8—N2	173.3 (10)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9···Iⁱ	0.93	3.06	3.795 (12)	138
C12—H12···Iⁱⁱ	0.93	3.03	3.929 (13)	162

Symmetry codes: (i) −x+1, y−1/2, −z+3/2; (ii) x−1/2, −y+3/2, −z+1.

Experimental details

Crystal data
Chemical formula	C₁₃H₁₃N₂⁺·I⁻
M_r	324.15
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	291
a, b, c (Å)	7.1690 (14), 12.399 (3), 15.026 (3)
V (Å³)	1335.6 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	2.37
Crystal size (mm)	0.30 × 0.10 × 0.10

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.536, 0.797
No. of measured, independent and observed [I > 2σ(I)] reflections	1408, 1408, 1015
R_int	0.000
(sin θ/λ)_max (Å⁻¹)	0.601

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.048, 0.125, 1.08
No. of reflections	1408
No. of parameters	146
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.10, −0.54
Absolute structure	Flack (1983), with no Friedel pairs
Absolute structure parameter	0.05 (10)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9···Iⁱ	0.93	3.06	3.795 (12)	138.00
C12—H12···Iⁱⁱ	0.93	3.03	3.929 (13)	162.00

Symmetry codes: (i) −x+1, y−1/2, −z+3/2; (ii) x−1/2, −y+3/2, −z+1.

Acknowledgements

The authors thank the Center for 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
Enraf–Nonius (1989). CAD-4 Software. Enraf–Nonius, Delft, The Netherlands. Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Harms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany. Google Scholar
North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359. CrossRef IUCr Journals Web of Science Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar