2-Amino­pyridinium (2-amino­pyridine)trichloridonickelate(II)

Hoong-Kun Fun; S Franklin; Samuel Robinson Jebas; T Balasubramanian

doi:10.1107/S1600536808005655

. 2008 Mar 5;64(Pt 4):m520–m521. doi: 10.1107/S1600536808005655

2-Aminopyridinium (2-aminopyridine)trichloridonickelate(II)

Hoong-Kun Fun ^a,^*, S Franklin ^b, Samuel Robinson Jebas ^a,^‡, T Balasubramanian ^b

PMCID: PMC2961041 PMID: 21201988

Abstract

In the title compound, (C₅H₇N₂)[NiCl₃(C₅H₆N₂)], the Ni^II atom is four-coordinated by three chloride anions and one N atom of a 2-aminopyridine ligand, forming a distorted tetrahedral coordination. In the crystal structure, cations and complex anions are linked into chains along the a, b and c axes by N—H⋯Cl hydrogen bonds, leading to the formation of a three-dimensional framework.

Related literature

For related literature, see: Batsanov & Howard (2001 ▶); Bis & Zaworotko (2005 ▶); Chao et al. (1975 ▶); Corain et al. (1985 ▶); Jebas et al. (2006 ▶); Valdés-Martínez et al. (2001 ▶); Sletten & Kovacs (1993 ▶); Smith et al. (2000 ▶, 2001 ▶); Stibrany et al. (2004 ▶); Wei & Willett (1995 ▶); Windholz (1976 ▶).

Experimental

Crystal data

(C₅H₇N₂)[NiCl₃(C₅H₆N₂)]
M _r = 354.3
Monoclinic,
a = 12.9265 (1) Å
b = 8.0644 (1) Å
c = 13.9893 (1) Å
β = 106.163 (1)°
V = 1400.67 (2) Å³
Z = 4
Mo Kα radiation
μ = 1.94 mm⁻¹
T = 100.0 (1) K
0.37 × 0.08 × 0.07 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer with Oxford Cryosystems Cobra low-temperature attachment
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.533, T _max = 0.876
19539 measured reflections
6427 independent reflections
5088 reflections with I > 2σ(I)
R _int = 0.031

Refinement

R[F ² > 2σ(F ²)] = 0.035
wR(F ²) = 0.079
S = 1.05
6427 reflections
167 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.52 e Å⁻³
Δρ_min = −0.64 e Å⁻³
Absolute structure: Flack (1983 ▶), 1953 Friedel pairs
Flack parameter: 0.065 (9)

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: APEX2; data reduction: SAINT (Bruker, 2005 ▶); program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2003 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808005655/ci2566sup1.cif

e-64-0m520-sup1.cif^{(15.9KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808005655/ci2566Isup2.hkl

e-64-0m520-Isup2.hkl^{(308.2KB, hkl)}

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

Table 1. Selected geometric parameters (Å, °).

Ni1—N1	2.0287 (17)
Ni1—Cl2	2.2625 (6)
Ni1—Cl1	2.2665 (5)
Ni1—Cl3	2.2722 (6)

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N1—Ni1—Cl2	114.10 (5)
N1—Ni1—Cl1	109.21 (5)
Cl2—Ni1—Cl1	107.77 (2)
N1—Ni1—Cl3	104.63 (5)
Cl2—Ni1—Cl3	108.62 (2)
Cl1—Ni1—Cl3	112.60 (2)

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Table 2. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H1N3⋯Cl2ⁱ	0.82 (3)	2.81 (3)	3.380 (2)	128 (2)
N2—H2B⋯Cl2	0.86	2.53	3.3475 (19)	159
N2—H2C⋯Cl1ⁱⁱ	0.86	2.63	3.4866 (19)	172
N4—H4B⋯Cl3ⁱ	0.86	2.36	3.197 (2)	165
N4—H4C⋯Cl1ⁱⁱⁱ	0.86	2.54	3.344 (2)	156

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) .

Acknowledgments

HKF and SRJ thank the Malaysian Government and Universiti Sains Malaysia for the Science Fund grant No. 305/PFIZIK/613312. SRJ thanks Universiti Sains Malaysia for the award a postdoctoral research fellowship.

supplementary crystallographic information

Comment

2-Aminopyridine is used in the manufacture of pharmaceuticals, especially antihistaminic drugs (Windholz, 1976). As a part of our investigations on the binding modes of 2-aminopyridine with metals, we report here the crystal structure of 2-aminopyridinium (2-aminopyridine)trichloronickel(II).

The asymmetric unit of the title compound contains one 2-aminopyridinium cation and one (2-aminopyridine)trichloronickel(II) anion. Protonation of atom N3 of the uncomplexed 2-aminopyridine results in the widening of the C6—N3—C10 angle to 123.3 (2)°, which is 117.7 (1)° in neutral 2-aminopyridine (Chao et al., 1975). The bond lengths and angles are comparable with those observed in related structures (Bis & Zaworotko, 2005; Smith et al., 2000; Jebas et al., 2006).

In the monomeric complex, the Ni^II ion is four-coordinated by three Cl anions and the N atom of the 2-aminopyridine ligand, forming a distorted tetrahedral coordination (Fig 1). The Ni—Cl bond lengths (Table 1) are comparable with that reported in the literature (Valdés-Martínez et al., 2001; Batsanov et al., 2001; Sletten & Kovacs, 1993; Corain et al., 1985; Stibrany et al., 2004). The Cl—Ni—Cl bond angles (107.77 (2)° and 108.62 (2)°) are close to the values reported in the literature (Smith et al., 2001; Wei et al., 1995). The dihedral angle between the pyridine and pyridinium rings is 0.9 (2)°.

In the crystal structure, the cations and anionic complexes are stacked into chains along the a, b and c axes and are linked into a three-dimensional framework by N—H···Cl hydrogen bonds (Fig 2).

Experimental

Solutions of 2-aminopyridine and NiCl₂.2H₂O in water were mixed in a molar ratio of 2:1. Few drops of dilute hydrochloric acid were added to the solution and heated at 363 K for 2 h. Blue crystals of the title compound were obtained by slow evaporation after a period of one week.