4-Amino-3-ammonio­pyridinium dichloride

Qin, J.-H.; Wang, J.-G.

doi:10.1107/S1600536808041962

organic compounds

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ISSN: 2056-9890

Volume 65| Part 1| January 2009| Page o131

doi:10.1107/S1600536808041962

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4-Amino-3-ammoniopyridinium dichloride

Jian-Hua Qin ^a ^* and Jian-Ge Wang ^a

^aCollege of Chemistry and Chemical Engineering, Luoyang Normal University, Luoyang 471022, People's Republic of China
^*Correspondence e-mail: jh_q128105@126.com

(Received 3 December 2008; accepted 10 December 2008; online 17 December 2008)

The anions and cations of the title compound, C₅H₉N₃²⁺·2Cl⁻, are connected by two chloride-bridged three-centered N—H⋯Cl hydrogen bonds into a three-dimensional network. The aromatic rings are not involved in stacking interactions.

Related literature

For bond distances and angles in pyridine, derived from microwave spectra, see: Sørensen et al. (1974 ). For details of the N—H⋯Cl hydrogen bond in 4,4′-bipyridine compounds, see: Iyere et al. (2003 ). For N—H⋯Cl and secondary interactions in pyridinium chlorides, see: Jones et al. (2002 ); in 4-acetylpyridinium chloride, see: Kochel (2005 ). For N—H⋯Cl and O—H⋯Cl contacts in a triphenyl-pyridinium chloride (1/1) adduct, see: Sykora & Cioffi (2007 ).

Experimental

Crystal data

C₅H₉N₃²⁺·2Cl⁻
M_r = 182.05
Monoclinic, P 2₁ /c
a = 8.362 (2) Å
b = 7.3218 (19) Å
c = 13.239 (3) Å
β = 92.065 (4)°
V = 810.0 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.73 mm⁻¹
T = 296 (2) K
0.41 × 0.31 × 0.07 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1997 ) T_min = 0.734, T_max = 0.948
3949 measured reflections
1494 independent reflections
1345 reflections with I > 2σ(I)
R_int = 0.014

Refinement

R[F² > 2σ(F²)] = 0.025
wR(F²) = 0.068
S = 1.14
1494 reflections
92 parameters
H-atom parameters constrained
Δρ_max = 0.24 e Å⁻³
Δρ_min = −0.25 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯Cl2ⁱ	0.89	2.22	3.1142 (15)	178
N1—H1B⋯Cl2ⁱⁱ	0.89	2.37	3.1754 (16)	151
N1—H1C⋯Cl1ⁱⁱⁱ	0.89	2.23	3.0790 (16)	160
N2—H2A⋯Cl1ⁱⁱ	0.86	2.39	3.2188 (17)	163
N2—H2B⋯Cl1^iv	0.86	2.42	3.2672 (17)	168
N3—H3⋯Cl2	0.86	2.59	3.2499 (16)	135
N3—H3⋯Cl2^v	0.86	2.70	3.3198 (16)	130
Symmetry codes: (i) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) x, y+1, z; (iii) $[-x, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iv) -x, -y+1, -z+1; (v) -x+1, -y, -z+1.

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; 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/S1600536808041962/si2142sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808041962/si2142Isup2.hkl

checkCIF report

Comment top

The title compound is a salt containing a diprotonated 3,4-diaminopyridine cation and two Cl^- anions (Fig. 1). The C1—N3—C5 bond angle is wider than that in pyridine (116.94 (3)°; Sørensen et al., 1974) which indicates that the pyridine ring N atom is protonated (Table 1). Also, the 4-amino N atom is protonated. The projection of the crystal packing along the b axis is shown in Fig. 2. The Cl^- anions and the 3,4-diaminopyridinium cations in the title compound are bonded by two chlorine-bridged, three-centered N—H···Cl hydrogen bonds into a three-dimensional network (Fig. 2, Table 2). Example structures of related compounds with two- and three-centered N—H···Cl hydrogen bonds are discussed by Iyere et al. (2003); Jones et al. (2002); Kochel (2005) and Sykora & Cioffi (2007).

Related literature top

For bond distances and angles in pyridine, derived from microwave spectra, see: Sørensen et al. (1974). For details of the N—H···Cl hydrogen bond in 4,4'-bipyridine compounds, see: Iyere et al. (2003). For N—H···Cl and secondary interactions in pyridinium chlorides, see: Jones et al. (2002); in 4-acetylpyridinium chloride, see: Kochel (2005). For N—H···Cl and O—H···Cl contacts in a triphenyl-pyridinium chloride (1/1) adduct, see: Sykora & Cioffi (2007).

Experimental top

3,4-diaminopyridine (0.01 mmol) and HCl (0.02 mmol) in 10 ml ethanol. Suitable crystals for X-ray analysis, were grown by allowing the solution to slowly evaporate for 15 days, and were subsequently filtered off, washed with methanol and dried under air.

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); 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 asymmetric unit of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. A view of the title compound packing down the b axis.

4-Amino-3-ammoniopyridinium dichloride top

Crystal data top

C₅H₉N₃²⁺·2Cl⁻	F(000) = 376
M_r = 182.05	D_x = 1.493 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2439 reflections
a = 8.362 (2) Å	θ = 3.1–28.2°
b = 7.3218 (19) Å	µ = 0.73 mm⁻¹
c = 13.239 (3) Å	T = 296 K
β = 92.065 (4)°	Block, colorless
V = 810.0 (4) Å³	0.41 × 0.31 × 0.07 mm
Z = 4

Data collection top

Bruker SMART CCD area-detector diffractometer	1494 independent reflections
Radiation source: fine-focus sealed tube	1345 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.014
ϕ and ω scans	θ_max = 25.5°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS; Bruker, 1997)	h = −10→9
T_min = 0.734, T_max = 0.948	k = −6→8
3949 measured reflections	l = −16→15

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)] = 0.025	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.068	H-atom parameters constrained
S = 1.14	w = 1/[σ²(F_o²) + (0.0285P)² + 0.2927P] where P = (F_o² + 2F_c²)/3
1494 reflections	(Δ/σ)_max = 0.001
92 parameters	Δρ_max = 0.24 e Å⁻³
0 restraints	Δρ_min = −0.25 e Å⁻³

Crystal data top

C₅H₉N₃²⁺·2Cl⁻	V = 810.0 (4) Å³
M_r = 182.05	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 8.362 (2) Å	µ = 0.73 mm⁻¹
b = 7.3218 (19) Å	T = 296 K
c = 13.239 (3) Å	0.41 × 0.31 × 0.07 mm
β = 92.065 (4)°

Data collection top

Bruker SMART CCD area-detector diffractometer	1494 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 1997)	1345 reflections with I > 2σ(I)
T_min = 0.734, T_max = 0.948	R_int = 0.014
3949 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.025	0 restraints
wR(F²) = 0.068	H-atom parameters constrained
S = 1.14	Δρ_max = 0.24 e Å⁻³
1494 reflections	Δρ_min = −0.25 e Å⁻³
92 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Cl1	0.05806 (5)	0.10977 (6)	0.30663 (3)	0.03884 (15)
Cl2	0.51526 (5)	0.00029 (6)	0.35359 (3)	0.03603 (14)
N1	0.26647 (16)	0.68257 (19)	0.30328 (10)	0.0320 (3)
H1A	0.3291	0.6281	0.2594	0.048*
H1B	0.3026	0.7949	0.3160	0.048*
H1C	0.1670	0.6887	0.2772	0.048*
N2	0.11914 (19)	0.8105 (2)	0.48188 (12)	0.0439 (4)
H2A	0.1182	0.8773	0.4284	0.053*
H2B	0.0737	0.8485	0.5352	0.053*
N3	0.33856 (18)	0.3102 (2)	0.48536 (11)	0.0376 (4)
H3	0.3861	0.2061	0.4869	0.045*
C1	0.3383 (2)	0.4103 (2)	0.40010 (13)	0.0329 (4)
H1	0.3866	0.3649	0.3431	0.039*
C2	0.26762 (18)	0.5778 (2)	0.39701 (12)	0.0271 (3)
C3	0.19067 (19)	0.6488 (2)	0.48205 (12)	0.0296 (4)
C4	0.1921 (2)	0.5357 (2)	0.56891 (13)	0.0366 (4)
H4	0.1422	0.5751	0.6267	0.044*
C5	0.2655 (2)	0.3703 (2)	0.56862 (14)	0.0391 (4)
H5	0.2656	0.2976	0.6262	0.047*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0414 (3)	0.0428 (3)	0.0324 (2)	0.00951 (19)	0.00267 (18)	−0.00166 (18)
Cl2	0.0410 (3)	0.0298 (2)	0.0379 (2)	0.00388 (17)	0.01080 (18)	0.00231 (17)
N1	0.0335 (7)	0.0344 (8)	0.0283 (7)	0.0006 (6)	0.0044 (6)	−0.0002 (6)
N2	0.0617 (10)	0.0360 (8)	0.0348 (8)	0.0202 (8)	0.0147 (7)	0.0032 (7)
N3	0.0403 (8)	0.0265 (7)	0.0462 (9)	0.0089 (6)	0.0023 (7)	0.0007 (6)
C1	0.0319 (9)	0.0323 (9)	0.0346 (9)	0.0018 (7)	0.0031 (7)	−0.0054 (7)
C2	0.0260 (8)	0.0283 (8)	0.0270 (8)	−0.0013 (6)	0.0012 (6)	−0.0008 (6)
C3	0.0309 (8)	0.0274 (8)	0.0306 (8)	0.0029 (7)	0.0017 (7)	−0.0016 (7)
C4	0.0434 (10)	0.0377 (10)	0.0291 (9)	0.0069 (8)	0.0069 (7)	0.0021 (7)
C5	0.0459 (10)	0.0366 (10)	0.0349 (10)	0.0038 (8)	0.0013 (8)	0.0077 (8)

Geometric parameters (Å, º) top

N1—C2	1.458 (2)	N3—H3	0.8600
N1—H1A	0.8900	C1—C2	1.361 (2)
N1—H1B	0.8900	C1—H1	0.9300
N1—H1C	0.8900	C2—C3	1.416 (2)
N2—C3	1.326 (2)	C3—C4	1.417 (2)
N2—H2A	0.8600	C4—C5	1.358 (3)
N2—H2B	0.8600	C4—H4	0.9300
N3—C1	1.346 (2)	C5—H5	0.9300
N3—C5	1.353 (2)

C2—N1—H1A	109.5	C2—C1—H1	119.9
C2—N1—H1B	109.5	C1—C2—C3	121.06 (15)
H1A—N1—H1B	109.5	C1—C2—N1	119.26 (14)
C2—N1—H1C	109.5	C3—C2—N1	119.65 (14)
H1A—N1—H1C	109.5	N2—C3—C2	122.95 (15)
H1B—N1—H1C	109.5	N2—C3—C4	120.92 (15)
C3—N2—H2A	120.0	C2—C3—C4	116.12 (15)
C3—N2—H2B	120.0	C5—C4—C3	120.64 (16)
H2A—N2—H2B	120.0	C5—C4—H4	119.7
C1—N3—C5	121.29 (15)	C3—C4—H4	119.7
C1—N3—H3	119.4	N3—C5—C4	120.64 (16)
C5—N3—H3	119.4	N3—C5—H5	119.7
N3—C1—C2	120.23 (16)	C4—C5—H5	119.7
N3—C1—H1	119.9

C5—N3—C1—C2	1.9 (3)	N1—C2—C3—C4	177.72 (15)
N3—C1—C2—C3	−1.2 (2)	N2—C3—C4—C5	179.99 (18)
N3—C1—C2—N1	−178.99 (14)	C2—C3—C4—C5	0.7 (3)
C1—C2—C3—N2	−179.35 (16)	C1—N3—C5—C4	−1.2 (3)
N1—C2—C3—N2	−1.6 (2)	C3—C4—C5—N3	−0.1 (3)
C1—C2—C3—C4	−0.1 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···Cl2ⁱ	0.89	2.22	3.1142 (15)	178
N1—H1B···Cl2ⁱⁱ	0.89	2.37	3.1754 (16)	151
N1—H1C···Cl1ⁱⁱⁱ	0.89	2.23	3.0790 (16)	160
N2—H2A···Cl1ⁱⁱ	0.86	2.39	3.2188 (17)	163
N2—H2B···Cl1^iv	0.86	2.42	3.2672 (17)	168
N3—H3···Cl2	0.86	2.59	3.2499 (16)	135
N3—H3···Cl2^v	0.86	2.70	3.3198 (16)	130

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

Experimental details

Crystal data
Chemical formula	C₅H₉N₃²⁺·2Cl⁻
M_r	182.05
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	8.362 (2), 7.3218 (19), 13.239 (3)
β (°)	92.065 (4)
V (Å³)	810.0 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.73
Crystal size (mm)	0.41 × 0.31 × 0.07

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 1997)
T_min, T_max	0.734, 0.948
No. of measured, independent and observed [I > 2σ(I)] reflections	3949, 1494, 1345
R_int	0.014
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.025, 0.068, 1.14
No. of reflections	1494
No. of parameters	92
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.24, −0.25

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), 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
N1—H1A···Cl2ⁱ	0.89	2.22	3.1142 (15)	178.0
N1—H1B···Cl2ⁱⁱ	0.89	2.37	3.1754 (16)	150.9
N1—H1C···Cl1ⁱⁱⁱ	0.89	2.23	3.0790 (16)	160.3
N2—H2A···Cl1ⁱⁱ	0.86	2.39	3.2188 (17)	163.2
N2—H2B···Cl1^iv	0.86	2.42	3.2672 (17)	168.3
N3—H3···Cl2	0.86	2.59	3.2499 (16)	134.7
N3—H3···Cl2^v	0.86	2.70	3.3198 (16)	130.0

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

Acknowledgements

The authors thank Luo Yang Normal University for supporting this work.

References

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