2-Amino-5-cyano­pyridinium chloride

Abstract

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,

• a = 4.0937 (8) Å

• b = 11.856 (2) Å

• c = 14.842 (3) Å

• β = 94.95 (3)°

• V = 717.7 (2) ų

• 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[F ² > 2σ(F ²)] = 0.045

• wR(F ²) = 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

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.

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

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) ; (ii) .

supplementary crystallographic information

Comment

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.

Experimental

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.

Refinement

All H atoms were fixed geometrically and treated as riding, with C–H = 0.93 Å, N–H =0.86 Å, and with U_iso(H) =1.2Ueq(C, N).

Figures

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.

Crystal data

C6H6N3+·Cl–	F000 = 320
Mr = 155.59	Dx = 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 = 2.3–24.4º
b = 11.856 (2) Å	µ = 0.45 mm−1
c = 14.842 (3) Å	T = 298 (2) K
β = 94.95 (3)º	Block, colourless
V = 717.7 (2) Å3	0.18 × 0.15 × 0.15 mm
Z = 4

Data collection

Rigaku Mercury2 diffractometer	1652 independent reflections
Radiation source: fine-focus sealed tube	1252 reflections with I > 2σ(I)
Monochromator: graphite	Rint = 0.044
Detector resolution: 13.6612 pixels mm-1	θmax = 27.5º
T = 298(2) K	θmin = 3.3º
ω scans	h = −5→5
Absorption correction: multi-scan(CrystalClear; Rigaku, 2005)	k = −15→15
Tmin = 0.922, Tmax = 0.935	l = −19→19
7307 measured reflections

Refinement

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)] = 0.045	H-atom parameters constrained
wR(F2) = 0.102	w = 1/[σ2(Fo2) + (0.041P)2 + 0.2213P] where P = (Fo2 + 2Fc2)/3
S = 1.06	(Δ/σ)max < 0.001
1652 reflections	Δρmax = 0.21 e Å−3
91 parameters	Δρmin = −0.23 e Å−3
Primary atom site location: structure-invariant direct methods	Extinction correction: none

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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, °)

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, °)

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.