2-Acetyl­pyridinium 3-amino-2-chloro­pyridinium tetra­chloridocobaltate(II)

Ariel Adamski; Violetta Patroniak; Maciej Kubicki

doi:10.1107/S1600536809000713

. 2009 Jan 10;65(Pt 2):m175–m176. doi: 10.1107/S1600536809000713

2-Acetylpyridinium 3-amino-2-chloropyridinium tetrachloridocobaltate(II)

Ariel Adamski ^a, Violetta Patroniak ^a, Maciej Kubicki ^a,^*

PMCID: PMC2968359 PMID: 21581781

Abstract

In the title complex, (C₅H₆ClN₂)(C₇H₈NO)[CoCl₄], the Co^II ions are tetrahedrally coordinated. The crystal structure is built from hydrogen-bonded centrosymmetric tetramers of tetrachloridocobaltate(II) dianions and 3-amino-2-chloropyridinium cations, additionally strengthened by significant π–π stacking of pyridinium rings [interplanar distance 3.389 (3) Å]. The tetramers are linked by N—H⋯Cl hydrogen bonds into chains; the second kind of cations, viz. 2-acetylpyridinium, are connected by N—H⋯Cl hydrogen bonds to both sides of the chain. The Co—Cl bond lengths in the dianion correlate with the number of hydrogen bonds accepted by the Cl atom. An intramolecular C—H⋯Cl interaction is also present.

Related literature

There are only few examples of structures involving the ligands present in the title structure. For related structures, see: 2-acetylpyridine itself (Laurent, 1966 ▶) and its cation in perchlorate (Husak, 1996 ▶) and in the complex with tetraphenylporphyrin-zinc(II) (Byrn et al., 1993 ▶), and a free base 3-amino-2-chloropyridine (Saha et al., 2006 ▶), and the latter as the dihydrogenphosphate (Hamed et al., 2007 ▶) and as the silver complexes (Tong et al., 2002 ▶; Li et al., 2002 ▶). For literature on the Schiff base complexes, see Häner & Hall (1999 ▶); Mukherjee et al. (2005 ▶); Radecka-Paryzek et al. (2005 ▶); Yam & Lo (1999 ▶).

Experimental

Crystal data

(C₅H₆ClN₂)(C₇H₈NO)[CoCl₄]
M _r = 452.44
Triclinic,
a = 7.3255 (5) Å
b = 8.3188 (5) Å
c = 16.2657 (11) Å
α = 89.114 (5)°
β = 82.806 (5)°
γ = 64.145 (6)°
V = 884.13 (10) Å³
Z = 2
Mo Kα radiation
μ = 1.73 mm⁻¹
T = 100 (1) K
0.4 × 0.15 × 0.1 mm

Data collection

Kuma KM-4-CCD four-circle diffractometer
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2007 ▶) T _min = 0.616, T _max = 0.841
10954 measured reflections
3798 independent reflections
3470 reflections with I > 2σ(I)
R _int = 0.019

Refinement

R[F ² > 2σ(F ²)] = 0.031
wR(F ²) = 0.065
S = 1.24
3798 reflections
216 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.70 e Å⁻³
Δρ_min = −0.36 e Å⁻³

Data collection: CrysAlis CCD (Oxford Diffraction, 2007 ▶); cell refinement: CrysAlis RED (Oxford Diffraction, 2007 ▶); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: Stereochemical Workstation Operation Manual (Siemens, 1989 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809000713/lx2085sup1.cif

e-65-0m175-sup1.cif^{(18KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809000713/lx2085Isup2.hkl

e-65-0m175-Isup2.hkl^{(182.4KB, hkl)}

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
N1B—H1B⋯Cl1	0.88 (3)	2.28 (4)	3.126 (2)	161 (3)
N1A—H1A⋯Cl2ⁱ	0.84 (3)	2.41 (3)	3.127 (2)	145 (3)
N31A—H31A⋯Cl2ⁱⁱ	0.90 (4)	2.51 (4)	3.323 (3)	151 (3)
N31A—H31B⋯Cl3	0.96 (4)	2.33 (4)	3.267 (3)	167 (3)
C6B—H6B⋯Cl4	0.95	2.71	3.647 (3)	171

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

Acknowledgments

This research was carried out as part of a Polish Ministry of Higher Education and Science project (grant No. NN 204 2716 33).

supplementary crystallographic information

Comment

Schiff bases are often employed as ligands in the metal ion - directed assembly of coordination architectures (Radecka-Paryzek et al., 2005). Such complexes are used as luminescent probes in the visible and near-IR spectral domains (Yam et al., 1999), as precursors for doped materials where metal centers must be implemented at a fixed distance and as catalysts for specific DNA (Mukherjee et al., 2005) and RNA (Häner & Hall, 1999) cleavage. In the course of our studies of Schiff base metal complexes with novel chemical properties we have accidentally synthesized the interesting example of three-component complex with CoCl₄ dianion and two different cations: 3-amino-chloropyridinium (a) and 2-acetylpyridinium (b) (Scheme & Fig. 1).

Both cations are planar within the experimental error; the maximum deviation from the least-squares planes are as small as 0.006 (2)Å in (a) and 0.002 (2)Å in (b). In the latter case the plane of acetyl group makes a dihedral angle of 11.0 (2)° with the ring plane. In the crystal structure, two motifs involving the (a) cations, R⁴₄(12) and R⁴₄(18, act together to make the double chain of these cations and dianions along [110] direction. The R⁴₄(18) motif is additionally strengthened by the π-π stacking of pyridinium rings. The distance between the exactly parallel least-squares planes is 3.389 (3) Å, with relatively small offset of only 0.708 Å. The second kind of cations, (b) are joined - by means of the N—H···Cl hydrogen bonds - to the chain, on its both sides (Fig. 2). Additionally, relatively short and linear C—H···Cl hydrogen bond is accepted by the Cl4 atom, not involved in any N—H···Cl interactions.

The Co is tetrahedrally coordinated in the anions (Fig. 1); the distortion from the ideal geometry is small. The angles are close to the ideal values {106.68 (3) - 112.35 (3)°}. The differences in the Co—Cl bond lengths correlate with the number of hydrogen bonds accepted by the Cl atom: Co—Cl2 bond is the longest {2.2893 (7) Å; Cl2 accepts two h.b.'s}, Co—Cl1 and Co—Cl3 have similar, intermediate lengths of 2.2751 (7)Å and 2.2771 (7) Å, and Cl4, which accepts only C—H···Cl hydrogen bonds, makes the shortest Co—Cl bond of 2.2593 (7) Å.

Experimental

To a mixture of cobalt chloride hexahydrate (18.2 mg; 0.08 mmol) and 2-acetylpyridine (9.4 mg; 0.08.m mol) in acetonitrile (20 cm³), 3-amino-2-chloropyridine (0.01 g; 0.08 mmol) in acetonitrile (10 cm³) was added dropwise with stirring. The reaction mixture was stirred for 24 h, at room temperature. The green crystals were obtained by slow diffusion of chloroform to the acetonitrile solution.