2-Amino-5-cyano­pyridinium nitrate

Dai, J.

doi:10.1107/S1600536808028031

organic compounds

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ISSN: 2056-9890

Volume 64| Part 10| October 2008| Page o1899

doi:10.1107/S1600536808028031

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2-Amino-5-cyanopyridinium nitrate

Jing Dai ^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 26 August 2008; accepted 2 September 2008; online 6 September 2008)

In the title compound, C₆H₆N₃⁺·NO₃⁻, the packing is consolidatedby N—H⋯N and N—H⋯O hydrogen bonds.

Related literature

For the chemisty of amine derivatives, see: Manzur et al. (2007 ); Ismayilov et al. (2007 ); Austria et al. (2007 ); Wen (2008 ).

Experimental

Crystal data

C₆H₆N₃⁺·NO₃⁻
M_r = 182.15
Monoclinic, P 2₁ /n
a = 4.6475 (9) Å
b = 12.713 (3) Å
c = 13.417 (3) Å
β = 97.91 (3)°
V = 785.1 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.13 mm⁻¹
T = 298 (2) K
0.25 × 0.15 × 0.15 mm

Data collection

Rigaku Mercury2 diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.975, T_max = 0.981
8053 measured reflections
1798 independent reflections
1163 reflections with I > 2σ(I)
R_int = 0.050

Refinement

R[F² > 2σ(F²)] = 0.053
wR(F²) = 0.127
S = 1.07
1798 reflections
142 parameters
All H-atom parameters refined
Δρ_max = 0.17 e Å⁻³
Δρ_min = −0.17 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2B⋯O2ⁱ	0.90 (2)	2.05 (3)	2.941 (3)	169 (2)
N1—H1⋯O1ⁱ	0.92 (3)	1.82 (3)	2.733 (2)	170 (2)
N2—H2C⋯O3	0.83 (3)	2.10 (3)	2.926 (3)	174 (3)
Symmetry code: (i) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

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 (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808028031/wk2092sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808028031/wk2092Isup2.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; Wen 2008). We report here the crystal structure of the title compound.

In the title compound (Fig. 1), the N1 atom of the pyridine ring is protonated. The nitrile group and the pyridinium ring are essentially coplanar. The nitrile group C6≡N3 bond length of 1.133 (3)Å is within the normal range. Crystal cohesion is enforced by N—H···N and N—H···O hydrogen bonds (Table 1, Fig. 2).

Related literature top

For the chemisty of amine derivatives, see: Manzur et al. (2007); Ismayilov et al. (2007); Austria et al. (2007); Wen (2008).

Experimental top

6-aminonicotinonitrile (3 mmol) was dissolved in the solution of ethanol (20 ml) and nitric acid (1 ml), and evaporated in the air affording colorless block crystals of this compound 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 (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (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. The crystal packing of the title compound viewed along the a axis and all hydrogen atoms not involved in hydrogen bonding (dashed lines) were omitted for clarity.

2-Amino-5-cyanopyridinium nitrate top

Crystal data top

C₆H₆N₃⁺·NO₃⁻	F(000) = 376
M_r = 182.15	D_x = 1.541 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 1796 reflections
a = 4.6475 (9) Å	θ = 3.1–27.5°
b = 12.713 (3) Å	µ = 0.13 mm⁻¹
c = 13.417 (3) Å	T = 298 K
β = 97.91 (3)°	Block, colourless
V = 785.1 (3) Å³	0.25 × 0.15 × 0.15 mm
Z = 4

Data collection top

Rigaku Mercury2 diffractometer	1798 independent reflections
Radiation source: fine-focus sealed tube	1163 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.050
Detector resolution: 13.6612 pixels mm^-1	θ_max = 27.5°, θ_min = 3.1°
ω scans	h = −6→6
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −16→16
T_min = 0.975, T_max = 0.981	l = −17→17
8053 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)] = 0.053	Hydrogen site location: difference Fourier map
wR(F²) = 0.127	All H-atom parameters refined
S = 1.07	w = 1/[σ²(F_o²) + (0.0514P)² + 0.1542P] where P = (F_o² + 2F_c²)/3
1798 reflections	(Δ/σ)_max < 0.001
142 parameters	Δρ_max = 0.17 e Å⁻³
0 restraints	Δρ_min = −0.17 e Å⁻³

Crystal data top

C₆H₆N₃⁺·NO₃⁻	V = 785.1 (3) Å³
M_r = 182.15	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 4.6475 (9) Å	µ = 0.13 mm⁻¹
b = 12.713 (3) Å	T = 298 K
c = 13.417 (3) Å	0.25 × 0.15 × 0.15 mm
β = 97.91 (3)°

Data collection top

Rigaku Mercury2 diffractometer	1798 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	1163 reflections with I > 2σ(I)
T_min = 0.975, T_max = 0.981	R_int = 0.050
8053 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.053	0 restraints
wR(F²) = 0.127	All H-atom parameters refined
S = 1.07	Δρ_max = 0.17 e Å⁻³
1798 reflections	Δρ_min = −0.17 e Å⁻³
142 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
C2	0.7591 (5)	0.86151 (17)	0.31844 (17)	0.0428 (5)
N4	0.0550 (4)	0.94943 (14)	0.12683 (14)	0.0456 (5)
N2	0.4566 (4)	0.71680 (19)	0.25422 (16)	0.0509 (5)
O1	−0.1866 (3)	0.98288 (12)	0.08728 (13)	0.0604 (5)
O2	0.2162 (4)	1.00628 (14)	0.18518 (14)	0.0651 (5)
O3	0.1266 (4)	0.85819 (13)	0.10891 (13)	0.0610 (5)
N1	0.8152 (4)	0.69031 (15)	0.38842 (14)	0.0406 (4)
C3	0.9809 (5)	0.89511 (17)	0.38692 (17)	0.0435 (5)
C5	1.0356 (4)	0.72284 (18)	0.45750 (17)	0.0402 (5)
C6	1.3541 (5)	0.86115 (17)	0.53382 (18)	0.0476 (6)
C1	0.6718 (4)	0.75525 (16)	0.31857 (15)	0.0379 (5)
C4	1.1235 (4)	0.82498 (16)	0.45893 (16)	0.0388 (5)
N3	1.5342 (5)	0.89264 (16)	0.59161 (18)	0.0684 (7)
H5	1.126 (4)	0.6708 (16)	0.5011 (15)	0.036 (5)*
H2A	0.655 (4)	0.9049 (16)	0.2716 (15)	0.033 (5)*
H3	1.041 (4)	0.9695 (19)	0.3867 (16)	0.051 (6)*
H2B	0.401 (5)	0.650 (2)	0.2641 (17)	0.048 (7)*
H1	0.764 (5)	0.620 (2)	0.389 (2)	0.067 (8)*
H2C	0.370 (6)	0.761 (3)	0.216 (2)	0.082 (10)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C2	0.0473 (13)	0.0351 (11)	0.0432 (12)	0.0020 (9)	−0.0043 (11)	0.0098 (10)
N4	0.0556 (12)	0.0365 (10)	0.0425 (10)	0.0046 (9)	−0.0013 (9)	0.0013 (9)
N2	0.0512 (12)	0.0424 (12)	0.0529 (12)	−0.0048 (10)	−0.0146 (10)	0.0011 (10)
O1	0.0532 (10)	0.0445 (9)	0.0766 (12)	0.0102 (8)	−0.0156 (9)	−0.0064 (8)
O2	0.0615 (11)	0.0566 (11)	0.0698 (11)	0.0031 (8)	−0.0179 (9)	−0.0180 (9)
O3	0.0770 (12)	0.0405 (9)	0.0599 (11)	0.0171 (8)	−0.0098 (9)	−0.0044 (8)
N1	0.0405 (10)	0.0306 (10)	0.0478 (11)	−0.0032 (8)	−0.0041 (8)	0.0032 (8)
C3	0.0471 (13)	0.0323 (12)	0.0492 (13)	−0.0021 (10)	−0.0003 (11)	0.0029 (10)
C5	0.0394 (11)	0.0383 (12)	0.0408 (12)	0.0034 (9)	−0.0025 (10)	0.0052 (10)
C6	0.0495 (14)	0.0373 (12)	0.0515 (14)	−0.0002 (10)	−0.0089 (12)	0.0008 (10)
C1	0.0356 (11)	0.0399 (12)	0.0370 (11)	0.0027 (9)	0.0007 (9)	0.0003 (9)
C4	0.0355 (11)	0.0377 (12)	0.0414 (11)	−0.0002 (9)	−0.0014 (9)	0.0020 (10)
N3	0.0697 (14)	0.0501 (13)	0.0755 (16)	−0.0045 (11)	−0.0249 (13)	−0.0036 (11)

Geometric parameters (Å, º) top

C2—C3	1.352 (3)	N1—C5	1.348 (3)
C2—C1	1.411 (3)	N1—C1	1.354 (3)
C2—H2A	0.92 (2)	N1—H1	0.92 (3)
N4—O3	1.239 (2)	C3—C4	1.411 (3)
N4—O2	1.239 (2)	C3—H3	0.99 (2)
N4—O1	1.249 (2)	C5—C4	1.361 (3)
N2—C1	1.322 (3)	C5—H5	0.94 (2)
N2—H2B	0.90 (2)	C6—N3	1.133 (3)
N2—H2C	0.83 (3)	C6—C4	1.440 (3)

C3—C2—C1	119.6 (2)	C2—C3—H3	119.4 (13)
C3—C2—H2A	123.7 (12)	C4—C3—H3	120.0 (13)
C1—C2—H2A	116.7 (12)	N1—C5—C4	120.1 (2)
O3—N4—O2	120.89 (19)	N1—C5—H5	116.3 (12)
O3—N4—O1	119.08 (18)	C4—C5—H5	123.6 (12)
O2—N4—O1	120.00 (18)	N3—C6—C4	177.9 (2)
C1—N2—H2B	117.2 (15)	N2—C1—N1	118.9 (2)
C1—N2—H2C	115 (2)	N2—C1—C2	123.1 (2)
H2B—N2—H2C	127 (3)	N1—C1—C2	118.07 (19)
C5—N1—C1	123.0 (2)	C5—C4—C3	118.77 (19)
C5—N1—H1	117.7 (16)	C5—C4—C6	120.53 (19)
C1—N1—H1	119.4 (17)	C3—C4—C6	120.69 (19)
C2—C3—C4	120.5 (2)

C1—C2—C3—C4	−0.6 (3)	C3—C2—C1—N1	0.2 (3)
C1—N1—C5—C4	−0.2 (3)	N1—C5—C4—C3	−0.3 (3)
C5—N1—C1—N2	−179.4 (2)	N1—C5—C4—C6	178.5 (2)
C5—N1—C1—C2	0.2 (3)	C2—C3—C4—C5	0.6 (3)
C3—C2—C1—N2	179.8 (2)	C2—C3—C4—C6	−178.2 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2B···O2ⁱ	0.90 (2)	2.05 (3)	2.941 (3)	169 (2)
N1—H1···O1ⁱ	0.92 (3)	1.82 (3)	2.733 (2)	170 (2)
N1—H1···N4ⁱ	0.92 (3)	2.62 (3)	3.505 (3)	161 (2)
N2—H2C···O3	0.83 (3)	2.10 (3)	2.926 (3)	174 (3)

Symmetry code: (i) −x+1/2, y−1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₆H₆N₃⁺·NO₃⁻
M_r	182.15
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	298
a, b, c (Å)	4.6475 (9), 12.713 (3), 13.417 (3)
β (°)	97.91 (3)
V (Å³)	785.1 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.13
Crystal size (mm)	0.25 × 0.15 × 0.15

Data collection
Diffractometer	Rigaku Mercury2 diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.975, 0.981
No. of measured, independent and observed [I > 2σ(I)] reflections	8053, 1798, 1163
R_int	0.050
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.053, 0.127, 1.07
No. of reflections	1798
No. of parameters	142
H-atom treatment	All H-atom parameters refined
Δρ_max, Δρ_min (e Å⁻³)	0.17, −0.17

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2B···O2ⁱ	0.90 (2)	2.05 (3)	2.941 (3)	169 (2)
N1—H1···O1ⁱ	0.92 (3)	1.82 (3)	2.733 (2)	170 (2)
N1—H1···N4ⁱ	0.92 (3)	2.62 (3)	3.505 (3)	161 (2)
N2—H2C···O3	0.83 (3)	2.10 (3)	2.926 (3)	174 (3)

Symmetry code: (i) −x+1/2, 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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