2-Amino-5-chloro­pyridinium nitrate

Zaouali Zgolli, D.; Boughzala, H.; Driss, A.

doi:10.1107/S160053680904149X

organic compounds

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Volume 65| Part 11| November 2009| Page o2755

https://doi.org/10.1107/S160053680904149X

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2-Amino-5-chloropyridinium nitrate

Donia Zaouali Zgolli,^a Habib Boughzala ^a ^* and Ahmed Driss ^a

^aLaboratoire de Matériaux et Cristallochimie, Faculté des Sciences, El Manar, 2092 Tunis, Tunisia
^*Correspondence e-mail: donia_zgolli@hotmail.com

(Received 4 October 2009; accepted 11 October 2009; online 17 October 2009)

The title structure, C₅H₆ClN₂⁺·NO₃⁻, is held together by extensive hydrogen bonding between the NO₃⁻ ions and 2-amino-5-chloropyridinium H atoms. The cation–anion N—H⋯O hydrogen bonds link the ions into a zigzag- chain which develops parallel to the b axis. The structure may be compared with that of the related 2-amino-5-cyanopyridinium nitrate.

Related literature

For metal-organic frameworks involving amine derivatives, see: Manzur et al. (2007 ); Ismayilov et al. (2007 ); Austria et al. (2007 ). For related structures, see: Pourayoubi et al. (2007 ); Rademeyer (2005 , 2007 ); Dai (2008 ).

Experimental

Crystal data

C₅H₆ClN₂⁺·NO₃⁻
M_r = 191.58
Monoclinic, P 2₁ /c
a = 4.788 (4) Å
b = 13.029 (3) Å
c = 12.779 (2) Å
β = 101.445 (18)°
V = 781.3 (7) Å³
Z = 4
Mo Kα radiation
μ = 0.46 mm⁻¹
T = 299 K
0.40 × 0.40 × 0.20 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.838, T_max = 0.914
2057 measured reflections
1691 independent reflections
1312 reflections with I > 2σ(I)
R_int = 0.017
2 standard reflections frequency: 120 min intensity decay: none

Refinement

R[F² > 2σ(F²)] = 0.037
wR(F²) = 0.106
S = 1.02
1691 reflections
109 parameters
H-atom parameters constrained
Δρ_max = 0.19 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
N2—H2A⋯O3	0.86	2.05	2.900 (2)	169
N2—H2B⋯O1ⁱ	0.86	2.06	2.912 (2)	174
N3—H3⋯O2	0.86	1.94	2.800 (2)	179
Symmetry code: (i) $[-x-1, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994 ); cell refinement: CAD-4 EXPRESS; 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 ) and PLATON (Spek, 2009 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S160053680904149X/dn2495sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S160053680904149X/dn2495Isup2.hkl

checkCIF report

Comment top

Derivatives of the aminoacid are of considerable interest in biological activities and there has been an increased interest in the chemistry of amine derivatives because of the construction of novel metal-organic frameworks (Manzur et al., 2007; Ismayilov et al., 2007; Austria et al., 2007). The crystal structures of 2-amino-5-chloropyridine (Pourayoubi et al., 2007) and their 2-Amino-5-cyanopyridinium nitrate (Dai, 2008) and 2-Aminopyridinium nitrate (Rademeyer, 2007) have been reported in literature. In this paper, we present the X-ray single-crystal structure of 2- Amino-5-chloropyridinium nitrate (I).

The title compound (I) contains an organic cation and a (NO₃)^- anion (Fig1). The cation is roughly planar with the largest deviation from the mean plane being 0.0553 (9)Å. The NO3 anion is slightly twisted with respect to the pyridinium ring making a dihedral angle of 17.2 (1)°

The monoprotonated chloropyridinium cation (C₅H₆ClN₂)⁺and the nitrate anion (NO₃)^-are linked by N-H···O which forms a zig-zag like chain parallel to the b axis (Table 1, Fig 2).

The crystal structure of 2-Amino-5-cyanopyridinium nitrate (II) (Dai, 2008) was recently published. The title compound (I) and this related compound (II) are isostructural. In both molecules, the asymmetric unit contains an organic cation 2-Amino-5-Xpyridinium (X: chloride (I), C≡N nitrile (II)) and a nitrate anion. They have the same space group (P2₁/c) and they are characterized by two-dimensional hydrogen-bonded networks.

The distances and angles of the present 2-amino-5-chloropyridinium nitrate molecule are consistent with the values reported in the literature of 2-aminopyridinium nitrate and 4-aminopyridinium nitrate molecules (Rademeyer 2005;2007).

Related literature top

For metal-organic frameworks involving amine derivatives, see: Manzur et al. (2007); Ismayilov et al. (2007); Austria et al. (2007). For related structures, see: Pourayoubi et al. (2007); Rademeyer (2005, 2007); Dai (2008).

Experimental top

2-Amino-5-chloropridine was dissolved in the solution of methanol and nitric acid (0.5 ml). Yellow crystals were obtained after a month on slow evaporation.

Structure description top

The monoprotonated chloropyridinium cation (C₅H₆ClN₂)⁺and the nitrate anion (NO₃)^-are linked by N-H···O which forms a zig-zag like chain parallel to the b axis (Table 1, Fig 2).

For metal-organic frameworks involving amine derivatives, see: Manzur et al. (2007); Ismayilov et al. (2007); Austria et al. (2007). For related structures, see: Pourayoubi et al. (2007); Rademeyer (2005, 2007); Dai (2008).

Computing details top

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994); cell refinement: CAD-4 EXPRESS (Enraf–Nonius, 1994); 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) and PLATON (Spek, 2009); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

	Fig. 1. Representation of the asymetric unit of 2-amino-5-chloropyridinium nitrate with the atom labeling scheme. Ellipsoids are drawn at the 30% probability level. H atoms are represented as small spheres of arbitrary radii. Hydrogen bonds are shown as dashed lines.
	Fig. 2. Partial packing view showing the formation of the zigzag chain parallel to the b axis. H atoms not involved in hydrogen bonding have been omitted for clarity.[Symmetry code: (i) -x-1, y+1/2, -z+3/2].

2-Amino-5-chloropyridinium nitrate top

Crystal data top

C₅H₆ClN₂⁺·NO₃⁻	F(000) = 392.0
M_r = 191.58	D_x = 1.620 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 25 reflections
a = 4.788 (4) Å	θ = 10–15°
b = 13.029 (3) Å	µ = 0.46 mm⁻¹
c = 12.779 (2) Å	T = 299 K
β = 101.445 (18)°	Prism, yellow
V = 781.3 (7) Å³	0.40 × 0.40 × 0.20 mm
Z = 4

Data collection top

Enraf–Nonius CAD-4 diffractometer	1312 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.017
Graphite monochromator	θ_max = 27.0°, θ_min = 2.3°
Nonprofiled ω/2θ scans	h = −1→6
Absorption correction: ψ scan (North et al., 1968)	k = −16→1
T_min = 0.838, T_max = 0.914	l = −16→15
2057 measured reflections	2 standard reflections every 120 min
1691 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)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.106	H-atom parameters constrained
S = 1.02	w = 1/[σ²(F_o²) + (0.0566P)² + 0.1965P] where P = (F_o² + 2F_c²)/3
1691 reflections	(Δ/σ)_max < 0.001
109 parameters	Δρ_max = 0.19 e Å⁻³
0 restraints	Δρ_min = −0.25 e Å⁻³

Crystal data top

C₅H₆ClN₂⁺·NO₃⁻	V = 781.3 (7) Å³
M_r = 191.58	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 4.788 (4) Å	µ = 0.46 mm⁻¹
b = 13.029 (3) Å	T = 299 K
c = 12.779 (2) Å	0.40 × 0.40 × 0.20 mm
β = 101.445 (18)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	1312 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.017
T_min = 0.838, T_max = 0.914	2 standard reflections every 120 min
2057 measured reflections	intensity decay: none
1691 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.037	0 restraints
wR(F²) = 0.106	H-atom parameters constrained
S = 1.02	Δρ_max = 0.19 e Å⁻³
1691 reflections	Δρ_min = −0.25 e Å⁻³
109 parameters

Special details top

Experimental. Number of psi-scan sets used was 3 Theta correction was applied. Averaged transmission function was used. No Fourier smoothing was applied (North et al., 1968).

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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	0.35469 (12)	0.37026 (4)	0.42068 (4)	0.0558 (2)
N1	−0.4403 (4)	−0.03452 (11)	0.63887 (12)	0.0404 (4)
N2	−0.2955 (4)	0.22776 (13)	0.73365 (13)	0.0484 (4)
H2A	−0.3487	0.1646	0.7301	0.058*
H2B	−0.3440	0.2679	0.7804	0.058*
N3	−0.0639 (3)	0.19881 (11)	0.59367 (12)	0.0373 (3)
H3	−0.1153	0.1356	0.5943	0.045*
C1	−0.1377 (4)	0.26344 (13)	0.66666 (13)	0.0349 (4)
C2	−0.0428 (4)	0.36615 (14)	0.66731 (15)	0.0399 (4)
H2	−0.0854	0.4122	0.7175	0.048*
C3	0.1112 (4)	0.39778 (15)	0.59430 (15)	0.0411 (4)
H3A	0.1751	0.4652	0.5950	0.049*
C4	0.1737 (4)	0.32811 (14)	0.51762 (14)	0.0373 (4)
C5	0.0878 (4)	0.22883 (14)	0.51921 (14)	0.0383 (4)
H5	0.1318	0.1819	0.4701	0.046*
O1	−0.5381 (3)	−0.12309 (10)	0.62043 (12)	0.0545 (4)
O2	−0.2376 (3)	−0.00614 (11)	0.59683 (13)	0.0523 (4)
O3	−0.5384 (4)	0.02366 (12)	0.70018 (14)	0.0635 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0681 (4)	0.0477 (3)	0.0615 (3)	−0.0101 (2)	0.0366 (3)	−0.0017 (2)
N1	0.0517 (9)	0.0326 (8)	0.0380 (8)	−0.0009 (7)	0.0115 (7)	0.0026 (6)
N2	0.0649 (10)	0.0414 (9)	0.0454 (9)	−0.0019 (8)	0.0269 (8)	−0.0030 (7)
N3	0.0455 (8)	0.0264 (7)	0.0427 (8)	−0.0034 (6)	0.0156 (7)	−0.0047 (6)
C1	0.0387 (9)	0.0339 (8)	0.0324 (8)	0.0019 (7)	0.0081 (7)	−0.0013 (7)
C2	0.0495 (10)	0.0318 (9)	0.0389 (9)	0.0003 (7)	0.0098 (8)	−0.0077 (7)
C3	0.0495 (10)	0.0290 (8)	0.0445 (10)	−0.0039 (7)	0.0088 (8)	−0.0051 (7)
C4	0.0384 (9)	0.0362 (9)	0.0396 (9)	−0.0013 (7)	0.0136 (7)	−0.0006 (7)
C5	0.0444 (9)	0.0333 (9)	0.0406 (9)	−0.0005 (7)	0.0171 (8)	−0.0082 (7)
O1	0.0784 (10)	0.0347 (7)	0.0552 (8)	−0.0152 (7)	0.0251 (8)	−0.0006 (6)
O2	0.0590 (9)	0.0369 (7)	0.0685 (9)	−0.0069 (6)	0.0308 (8)	−0.0010 (6)
O3	0.0788 (11)	0.0513 (9)	0.0708 (10)	−0.0089 (8)	0.0403 (9)	−0.0158 (8)

Geometric parameters (Å, º) top

Cl1—C4	1.7358 (19)	N3—H3	0.8600
N1—O3	1.247 (2)	C1—C2	1.413 (3)
N1—O1	1.250 (2)	C2—C3	1.363 (3)
N1—O2	1.255 (2)	C2—H2	0.9300
N2—C1	1.333 (2)	C3—C4	1.411 (3)
N2—H2A	0.8600	C3—H3A	0.9300
N2—H2B	0.8600	C4—C5	1.359 (3)
N3—C1	1.355 (2)	C5—H5	0.9300
N3—C5	1.364 (2)

O3—N1—O1	120.41 (17)	C3—C2—C1	119.96 (16)
O3—N1—O2	120.64 (16)	C3—C2—H2	120.0
O1—N1—O2	118.93 (16)	C1—C2—H2	120.0
C1—N2—H2A	120.0	C2—C3—C4	119.95 (17)
C1—N2—H2B	120.0	C2—C3—H3A	120.0
H2A—N2—H2B	120.0	C4—C3—H3A	120.0
C1—N3—C5	123.36 (15)	C5—C4—C3	119.70 (17)
C1—N3—H3	118.3	C5—C4—Cl1	120.49 (14)
C5—N3—H3	118.3	C3—C4—Cl1	119.80 (14)
N2—C1—N3	118.95 (16)	C4—C5—N3	119.23 (16)
N2—C1—C2	123.31 (16)	C4—C5—H5	120.4
N3—C1—C2	117.74 (15)	N3—C5—H5	120.4

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O3	0.86	2.05	2.900 (2)	169
N2—H2B···O1ⁱ	0.86	2.06	2.912 (2)	174
N3—H3···O2	0.86	1.94	2.800 (2)	179

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

Experimental details

Crystal data
Chemical formula	C₅H₆ClN₂⁺·NO₃⁻
M_r	191.58
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	299
a, b, c (Å)	4.788 (4), 13.029 (3), 12.779 (2)
β (°)	101.445 (18)
V (Å³)	781.3 (7)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.46
Crystal size (mm)	0.40 × 0.40 × 0.20

Data collection
Diffractometer	Enraf–Nonius CAD-4
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.838, 0.914
No. of measured, independent and observed [I > 2σ(I)] reflections	2057, 1691, 1312
R_int	0.017
(sin θ/λ)_max (Å⁻¹)	0.638

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.106, 1.02
No. of reflections	1691
No. of parameters	109
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.19, −0.25

Computer programs: CAD-4 EXPRESS (Enraf–Nonius, 1994), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2009), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O3	0.86	2.05	2.900 (2)	169.2
N2—H2B···O1ⁱ	0.86	2.06	2.912 (2)	173.5
N3—H3···O2	0.86	1.94	2.800 (2)	178.9

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

References

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CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 65| Part 11| November 2009| Page o2755

https://doi.org/10.1107/S160053680904149X

Open

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