2-Amino-5-cyano­pyridinium chloride

Wen, X.-C.

doi:10.1107/S1600536808020783

organic compounds

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ISSN: 2056-9890

Volume 64| Part 8| August 2008| Page o1461

doi:10.1107/S1600536808020783

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2-Amino-5-cyanopyridinium chloride

Xiao-Chun Wen ^a ^*

^aOrdered Matter Science Research Center, College of Chemistry and Chemical Engineering, Southeast University, Nanjing 210096, People's Republic of China
^*Correspondence e-mail: fudavid88@yahoo.com.cn

(Received 30 June 2008; accepted 4 July 2008; online 12 July 2008)

In the crystal structure of the title compound, C₆H₆N₃⁺·Cl⁻, cohesion is maintained by cation–anion N—H⋯Cl and cation–cation N—H⋯N hydrogen bonds, which link the ions into a three-dimensional network.

Related literature

For the use of tetrazole derivatives in coordination chemisty, see: Manzur et al. (2007 ); Ismayilov et al. (2007 ); Austria et al. (2007 ).

Experimental

Crystal data

C₆H₆N₃⁺·Cl⁻
M_r = 155.59
Monoclinic, P 2₁ /c
a = 4.0937 (8) Å
b = 11.856 (2) Å
c = 14.842 (3) Å
β = 94.95 (3)°
V = 717.7 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.45 mm⁻¹
T = 298 (2) K
0.18 × 0.15 × 0.15 mm

Data collection

Rigaku Mercury2 diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.922, T_max = 0.935
7307 measured reflections
1652 independent reflections
1252 reflections with I > 2σ(I)
R_int = 0.044

Refinement

R[F² > 2σ(F²)] = 0.045
wR(F²) = 0.102
S = 1.06
1652 reflections
91 parameters
H-atom parameters constrained
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.23 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯Cl1	0.86	2.29	3.0818 (18)	153
N3—H3A⋯Cl1	0.86	2.65	3.363 (2)	141
N3—H3A⋯N1ⁱ	0.86	2.53	3.046 (3)	120
N3—H3B⋯Cl1ⁱⁱ	0.86	2.37	3.216 (2)	167
Symmetry codes: (i) $[x+1, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (ii) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL/PC (Sheldrick, 2008); software used to prepare material for publication: SHELXTL/PC.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808020783/rz2232sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808020783/rz2232Isup2.hkl

checkCIF report

Comment top

In the past five years, we have focused on the chemistry of amine derivatives because of their multiple coordination modes as ligands to metal ions and for the construction of novel metal-organic frameworks (Manzur et al. 2007; Ismayilov et al. 2007; Austria et al. 2007). Herein the crystal structure of the title compound, 6-aminonicotinonitrile-1-ium chloride, is reported.

In the title compound (Fig.1), the N2 atom of the pyridine ring is protonated. The nitrile group and the pyridine ring are nearly coplanar, as indicated by the dihedral angle of 86.71 (14)° formed by the C≡N vector with the normal to the pyridine plane. Crystal cohesion is enforced by cation-anion N—H···Cl and cation-cation N—H···N hydrogen bonds (Table 1, Fig. 2) linking molecules into a three-dimensional network.

Related literature top

For the use of tetrazole derivatives in coordination chemisty, see: Manzur et al. (2007); Ismayilov et al. (2007); Austria et al. (2007).

Experimental top

6-Aminonicotinonitrile-1-ium chloride (3 mmol) was dissolved in ethanol (20 ml) and evaporated in the air affording colourless block-shaped crystals suitable for X-ray analysis.

Computing details top

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL/PC (Sheldrick, 2008); software used to prepare material for publication: SHELXTL/PC (Sheldrick, 2008).

Figures top

	Fig. 1. A view of the title compound with the atom-numbering scheme. Displacement ellipsoids were drawn at the 30% probability level.
	Fig. 2. Partial crystal packing of the title compound viewed along the a axis showing H bonding pattern as dashed lines. Hydrogen atoms not involved in hydrogen bonding are omitted for clarity.

2-Amino-5-cyanopyridinium chloride top

Crystal data top

C₆H₆N₃⁺·Cl⁻	F(000) = 320
M_r = 155.59	D_x = 1.440 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1250 reflections
a = 4.0937 (8) Å	θ = 2.3–24.4°
b = 11.856 (2) Å	µ = 0.45 mm⁻¹
c = 14.842 (3) Å	T = 298 K
β = 94.95 (3)°	Block, colourless
V = 717.7 (2) Å³	0.18 × 0.15 × 0.15 mm
Z = 4

Data collection top

Rigaku Mercury2 diffractometer	1652 independent reflections
Radiation source: fine-focus sealed tube	1252 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.044
Detector resolution: 13.6612 pixels mm^-1	θ_max = 27.5°, θ_min = 3.3°
ω scans	h = −5→5
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −15→15
T_min = 0.922, T_max = 0.935	l = −19→19
7307 measured reflections

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)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.102	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.041P)² + 0.2213P] where P = (F_o² + 2F_c²)/3
1652 reflections	(Δ/σ)_max < 0.001
91 parameters	Δρ_max = 0.21 e Å⁻³
0 restraints	Δρ_min = −0.23 e Å⁻³

Crystal data top

C₆H₆N₃⁺·Cl⁻	V = 717.7 (2) Å³
M_r = 155.59	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 4.0937 (8) Å	µ = 0.45 mm⁻¹
b = 11.856 (2) Å	T = 298 K
c = 14.842 (3) Å	0.18 × 0.15 × 0.15 mm
β = 94.95 (3)°

Data collection top

Rigaku Mercury2 diffractometer	1652 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	1252 reflections with I > 2σ(I)
T_min = 0.922, T_max = 0.935	R_int = 0.044
7307 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.045	0 restraints
wR(F²) = 0.102	H-atom parameters constrained
S = 1.06	Δρ_max = 0.21 e Å⁻³
1652 reflections	Δρ_min = −0.23 e Å⁻³
91 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
Cl1	0.44244 (14)	0.60704 (5)	0.17252 (4)	0.0459 (2)
N2	0.0652 (4)	0.69979 (14)	0.32749 (11)	0.0377 (4)
H2A	0.1041	0.6650	0.2787	0.045*
C2	−0.0884 (5)	0.64335 (18)	0.39019 (14)	0.0385 (5)
H2B	−0.1506	0.5687	0.3801	0.046*
N3	0.3183 (5)	0.85595 (16)	0.27271 (13)	0.0507 (5)
H3A	0.3567	0.8175	0.2256	0.061*
H3B	0.3816	0.9250	0.2777	0.061*
C3	−0.1527 (5)	0.69550 (17)	0.46837 (13)	0.0352 (5)
C1	−0.3034 (6)	0.63422 (18)	0.53757 (15)	0.0442 (5)
C6	0.1619 (5)	0.80885 (17)	0.33739 (13)	0.0355 (5)
C4	−0.0595 (5)	0.81008 (17)	0.48174 (14)	0.0398 (5)
H4A	−0.1029	0.8471	0.5346	0.048*
N1	−0.4184 (6)	0.58515 (18)	0.59282 (14)	0.0626 (6)
C5	0.0921 (5)	0.86506 (17)	0.41756 (15)	0.0414 (5)
H5A	0.1510	0.9403	0.4261	0.050*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0522 (3)	0.0472 (3)	0.0398 (3)	0.0063 (3)	0.0124 (2)	−0.0055 (2)
N2	0.0471 (10)	0.0364 (9)	0.0305 (9)	−0.0004 (8)	0.0091 (7)	−0.0073 (7)
C2	0.0442 (12)	0.0344 (11)	0.0376 (11)	−0.0020 (9)	0.0082 (9)	−0.0007 (9)
N3	0.0672 (13)	0.0442 (11)	0.0435 (11)	−0.0080 (10)	0.0207 (10)	−0.0001 (9)
C3	0.0370 (11)	0.0378 (11)	0.0313 (10)	0.0033 (9)	0.0063 (8)	0.0016 (8)
C1	0.0523 (13)	0.0414 (12)	0.0400 (12)	0.0027 (10)	0.0101 (10)	−0.0022 (10)
C6	0.0370 (11)	0.0366 (11)	0.0332 (10)	0.0022 (9)	0.0054 (9)	0.0028 (8)
C4	0.0486 (12)	0.0384 (11)	0.0334 (11)	0.0036 (10)	0.0104 (9)	−0.0066 (9)
N1	0.0862 (16)	0.0547 (13)	0.0514 (12)	−0.0085 (11)	0.0316 (12)	0.0009 (10)
C5	0.0530 (13)	0.0306 (11)	0.0419 (12)	−0.0015 (9)	0.0106 (10)	−0.0060 (9)

Geometric parameters (Å, º) top

N2—C2	1.345 (2)	C3—C4	1.420 (3)
N2—C6	1.356 (3)	C3—C1	1.440 (3)
N2—H2A	0.8600	C1—N1	1.140 (3)
C2—C3	1.360 (3)	C6—C5	1.414 (3)
C2—H2B	0.9300	C4—C5	1.349 (3)
N3—C6	1.323 (3)	C4—H4A	0.9300
N3—H3A	0.8600	C5—H5A	0.9300
N3—H3B	0.8600

C2—N2—C6	123.26 (17)	C4—C3—C1	120.62 (18)
C2—N2—H2A	118.4	N1—C1—C3	179.0 (3)
C6—N2—H2A	118.4	N3—C6—N2	118.60 (18)
N2—C2—C3	120.02 (19)	N3—C6—C5	123.9 (2)
N2—C2—H2B	120.0	N2—C6—C5	117.53 (18)
C3—C2—H2B	120.0	C5—C4—C3	119.85 (18)
C6—N3—H3A	120.0	C5—C4—H4A	120.1
C6—N3—H3B	120.0	C3—C4—H4A	120.1
H3A—N3—H3B	120.0	C4—C5—C6	120.34 (19)
C2—C3—C4	118.98 (18)	C4—C5—H5A	119.8
C2—C3—C1	120.37 (19)	C6—C5—H5A	119.8

C6—N2—C2—C3	−0.3 (3)	C2—C3—C4—C5	−0.4 (3)
N2—C2—C3—C4	0.9 (3)	C1—C3—C4—C5	177.6 (2)
N2—C2—C3—C1	−177.1 (2)	C3—C4—C5—C6	−0.7 (3)
C2—N2—C6—N3	178.4 (2)	N3—C6—C5—C4	−177.9 (2)
C2—N2—C6—C5	−0.8 (3)	N2—C6—C5—C4	1.2 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···Cl1	0.86	2.29	3.0818 (18)	153
N3—H3A···Cl1	0.86	2.65	3.363 (2)	141
N3—H3A···N1ⁱ	0.86	2.53	3.046 (3)	120
N3—H3B···Cl1ⁱⁱ	0.86	2.37	3.216 (2)	167

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

Experimental details

Crystal data
Chemical formula	C₆H₆N₃⁺·Cl⁻
M_r	155.59
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	298
a, b, c (Å)	4.0937 (8), 11.856 (2), 14.842 (3)
β (°)	94.95 (3)
V (Å³)	717.7 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.45
Crystal size (mm)	0.18 × 0.15 × 0.15

Data collection
Diffractometer	Rigaku Mercury2 diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.922, 0.935
No. of measured, independent and observed [I > 2σ(I)] reflections	7307, 1652, 1252
R_int	0.044
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.102, 1.06
No. of reflections	1652
No. of parameters	91
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.21, −0.23

Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL/PC (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···Cl1	0.86	2.29	3.0818 (18)	152.8
N3—H3A···Cl1	0.86	2.65	3.363 (2)	141.2
N3—H3A···N1ⁱ	0.86	2.53	3.046 (3)	119.8
N3—H3B···Cl1ⁱⁱ	0.86	2.37	3.216 (2)	166.9

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

Acknowledgements

This work was supported by a Start-up Grant from Southeast University to Professor Ren-Gen Xiong.

References

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