1-(Benzyl­ideneamino)pyridinum iodide

Cui, Y.-T.; Wang, J.-Q.; Ji, C.-X.; Wu, C.-R.; Guo, C.

doi:10.1107/S1600536808043717

organic compounds

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ISSN: 2056-9890

Volume 65| Part 2| February 2009| Page o229

doi:10.1107/S1600536808043717

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1-(Benzylideneamino)pyridinum iodide

Yong-Tao Cui,^a Jian-Qiang Wang,^a Chun-Xiang Ji,^a Cong-Ren Wu ^a and Cheng Guo ^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 18 December 2008; accepted 23 December 2008; online 8 January 2009)

In the title compound, C₁₂H₁₁N₂⁺·I⁻, the aromatic rings are oriented at a dihedral angle of 73.40 (3)°. In the crystal structure, π–π contacts between the pyridine rings and the benzene and pyridine rings [centroid–centroid distances = 3.548 (3) and 4.211 (3) Å] may stabilize the structure.

Related literature

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

Experimental

Crystal data

C₁₂H₁₁N₂⁺·I⁻
M_r = 310.13
Monoclinic, P 2₁ /c
a = 10.5722 (17) Å
b = 7.8219 (13) Å
c = 15.386 (3) Å
β = 108.354 (2)°
V = 1207.6 (4) Å³
Z = 4
Mo Kα radiation
μ = 2.62 mm⁻¹
T = 291 (2) K
0.13 × 0.12 × 0.10 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.727, T_max = 0.780
5768 measured reflections
2133 independent reflections
1713 reflections with I > 2σ(I)
R_int = 0.067
3 standard reflections frequency: 120 min intensity decay: none

Refinement

R[F² > 2σ(F²)] = 0.030
wR(F²) = 0.075
S = 0.94
2133 reflections
136 parameters
H-atom parameters constrained
Δρ_max = 0.50 e Å⁻³
Δρ_min = −0.53 e Å⁻³

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/S1600536808043717/hk2601sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808043717/hk2601Isup2.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 73.40 (3)°.

In the crystal structure, π-π contacts between the pyridine and the benzene rings and the pyridine rings, Cg1—Cg2ⁱ and Cg1—Cg1ⁱⁱ [symmetry codes: (i) x, 3/2 - y, z - 1/2; (ii) 1 - x, 2 - y, -z, where Cg1 and Cg2 are centroids of the rings A (N1/C1-C5) and B (C7-C12) , respectively] may stabilize the structure, with centroid-centroid distances of 3.548 (3) Å and 4.211 (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), benzaldehyde(10.6 g, 0.10 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; 21.7 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.

1-(Benzylideneamino)pyridinum iodide top

Crystal data top

C₁₂H₁₁N₂⁺·I⁻	F(000) = 600
M_r = 310.13	D_x = 1.706 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 25 reflections
a = 10.5722 (17) Å	θ = 2.1–25.3°
b = 7.8219 (13) Å	µ = 2.62 mm⁻¹
c = 15.386 (3) Å	T = 291 K
β = 108.354 (2)°	Block, yellow
V = 1207.6 (4) Å³	0.13 × 0.12 × 0.10 mm
Z = 4

Data collection top

Enraf–Nonius CAD-4 diffractometer	1713 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.067
Graphite monochromator	θ_max = 25.0°, θ_min = 2.8°
ω/2θ scans	h = −12→12
Absorption correction: ψ scan (North et al., 1968)	k = −9→7
T_min = 0.727, T_max = 0.780	l = −18→18
5768 measured reflections	3 standard reflections every 120 min
2133 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)] = 0.030	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.075	H-atom parameters constrained
S = 0.94	w = 1/[σ²(F_o²) + (0.0365P)²] where P = (F_o² + 2F_c²)/3
2133 reflections	(Δ/σ)_max = 0.001
136 parameters	Δρ_max = 0.50 e Å⁻³
0 restraints	Δρ_min = −0.53 e Å⁻³

Crystal data top

C₁₂H₁₁N₂⁺·I⁻	V = 1207.6 (4) Å³
M_r = 310.13	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 10.5722 (17) Å	µ = 2.62 mm⁻¹
b = 7.8219 (13) Å	T = 291 K
c = 15.386 (3) Å	0.13 × 0.12 × 0.10 mm
β = 108.354 (2)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	1713 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.067
T_min = 0.727, T_max = 0.780	3 standard reflections every 120 min
5768 measured reflections	intensity decay: none
2133 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.030	0 restraints
wR(F²) = 0.075	H-atom parameters constrained
S = 0.94	Δρ_max = 0.50 e Å⁻³
2133 reflections	Δρ_min = −0.53 e Å⁻³
136 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	0.36542 (2)	0.37261 (3)	0.175113 (16)	0.05509 (13)
N1	0.2501 (3)	0.8944 (3)	0.03899 (19)	0.0462 (7)
N2	0.1744 (3)	0.8956 (3)	0.10105 (19)	0.0482 (7)
C1	0.3602 (4)	0.7989 (5)	0.0544 (3)	0.0543 (9)
H1	0.3942	0.7393	0.1091	0.065*
C2	0.4222 (4)	0.7904 (5)	−0.0117 (3)	0.0597 (10)
H2	0.4975	0.7225	−0.0024	0.072*
C3	0.3734 (4)	0.8812 (5)	−0.0909 (3)	0.0586 (10)
H3	0.4162	0.8775	−0.1353	0.070*
C4	0.2612 (4)	0.9776 (6)	−0.1045 (2)	0.0633 (10)
H4	0.2274	1.0402	−0.1582	0.076*
C5	0.1982 (4)	0.9821 (5)	−0.0388 (2)	0.0617 (10)
H5	0.1205	1.0454	−0.0484	0.074*
C6	0.2447 (3)	0.9324 (4)	0.1829 (2)	0.0439 (8)
H6	0.3347	0.9579	0.1961	0.053*
C7	0.1831 (3)	0.9341 (5)	0.2553 (2)	0.0447 (8)
C8	0.2456 (4)	1.0226 (5)	0.3354 (2)	0.0584 (9)
H8	0.3250	1.0802	0.3419	0.070*
C9	0.0654 (4)	0.8452 (5)	0.2465 (3)	0.0566 (10)
H9	0.0240	0.7838	0.1934	0.068*
C10	0.0110 (4)	0.8488 (5)	0.3166 (3)	0.0687 (12)
H10	−0.0678	0.7902	0.3109	0.082*
C11	0.0729 (5)	0.9391 (6)	0.3955 (3)	0.0748 (13)
H11	0.0352	0.9419	0.4425	0.090*
C12	0.1899 (5)	1.0252 (6)	0.4051 (3)	0.0716 (12)
H12	0.2315	1.0851	0.4588	0.086*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
I1	0.05786 (18)	0.0622 (2)	0.04976 (17)	−0.00118 (11)	0.02344 (12)	0.00535 (11)
N1	0.0537 (16)	0.0507 (17)	0.0363 (15)	−0.0039 (13)	0.0172 (13)	−0.0040 (13)
N2	0.0509 (16)	0.0610 (18)	0.0355 (15)	−0.0047 (13)	0.0176 (13)	−0.0016 (14)
C1	0.064 (2)	0.050 (2)	0.052 (2)	0.0022 (18)	0.0222 (18)	0.0048 (18)
C2	0.066 (2)	0.055 (2)	0.067 (3)	0.0024 (19)	0.034 (2)	−0.005 (2)
C3	0.069 (2)	0.066 (2)	0.050 (2)	−0.012 (2)	0.0314 (19)	−0.013 (2)
C4	0.067 (2)	0.082 (3)	0.0402 (19)	0.001 (2)	0.0172 (18)	0.010 (2)
C5	0.061 (2)	0.083 (3)	0.043 (2)	0.010 (2)	0.0183 (17)	0.004 (2)
C6	0.0466 (18)	0.0441 (19)	0.0398 (19)	0.0008 (14)	0.0118 (15)	0.0004 (15)
C7	0.0471 (19)	0.0505 (19)	0.0351 (18)	0.0047 (15)	0.0107 (15)	0.0027 (16)
C8	0.061 (2)	0.070 (3)	0.0405 (19)	0.0007 (19)	0.0111 (17)	−0.0024 (19)
C9	0.054 (2)	0.068 (3)	0.050 (2)	−0.0020 (17)	0.0190 (18)	0.0039 (18)
C10	0.067 (3)	0.078 (3)	0.074 (3)	0.003 (2)	0.040 (2)	0.012 (2)
C11	0.097 (3)	0.082 (3)	0.062 (3)	0.033 (3)	0.049 (3)	0.019 (3)
C12	0.098 (3)	0.078 (3)	0.039 (2)	0.015 (3)	0.022 (2)	−0.004 (2)

Geometric parameters (Å, º) top

N1—N2	1.426 (4)	C6—C7	1.457 (4)
C1—N1	1.340 (4)	C6—H6	0.9300
C1—C2	1.375 (5)	C7—C8	1.385 (5)
C1—H1	0.9300	C7—C9	1.394 (5)
C2—C3	1.364 (5)	C8—C12	1.377 (5)
C2—H2	0.9300	C8—H8	0.9300
C3—C4	1.365 (5)	C9—C10	1.374 (6)
C3—H3	0.9300	C9—H9	0.9300
C4—C5	1.374 (5)	C10—C11	1.378 (7)
C4—H4	0.9300	C10—H10	0.9300
C5—N1	1.339 (4)	C11—C12	1.375 (6)
C5—H5	0.9300	C11—H11	0.9300
C6—N2	1.277 (4)	C12—H12	0.9300

C5—N1—C1	122.2 (3)	N2—C6—H6	120.2
C5—N1—N2	116.0 (3)	C7—C6—H6	120.2
C1—N1—N2	121.6 (3)	C8—C7—C9	119.8 (3)
C6—N2—N1	112.8 (3)	C8—C7—C6	118.8 (3)
N1—C1—C2	119.1 (4)	C9—C7—C6	121.4 (3)
N1—C1—H1	120.4	C12—C8—C7	120.0 (4)
C2—C1—H1	120.4	C12—C8—H8	120.0
C3—C2—C1	120.1 (4)	C7—C8—H8	120.0
C3—C2—H2	119.9	C10—C9—C7	119.7 (4)
C1—C2—H2	119.9	C10—C9—H9	120.1
C2—C3—C4	119.3 (4)	C7—C9—H9	120.1
C2—C3—H3	120.3	C9—C10—C11	120.1 (4)
C4—C3—H3	120.3	C9—C10—H10	120.0
C3—C4—C5	120.1 (4)	C11—C10—H10	120.0
C3—C4—H4	119.9	C12—C11—C10	120.5 (4)
C5—C4—H4	119.9	C12—C11—H11	119.7
N1—C5—C4	119.2 (4)	C10—C11—H11	119.7
N1—C5—H5	120.4	C11—C12—C8	119.9 (4)
C4—C5—H5	120.4	C11—C12—H12	120.0
N2—C6—C7	119.7 (3)	C8—C12—H12	120.0

Experimental details

Crystal data
Chemical formula	C₁₂H₁₁N₂⁺·I⁻
M_r	310.13
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	291
a, b, c (Å)	10.5722 (17), 7.8219 (13), 15.386 (3)
β (°)	108.354 (2)
V (Å³)	1207.6 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	2.62
Crystal size (mm)	0.13 × 0.12 × 0.10

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.727, 0.780
No. of measured, independent and observed [I > 2σ(I)] reflections	5768, 2133, 1713
R_int	0.067
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.030, 0.075, 0.94
No. of reflections	2133
No. of parameters	136
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.50, −0.53

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

Acknowledgements

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

References

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North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359. CrossRef IUCr Journals Web of Science Google Scholar
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