Bis[4-amino-3,5-bis­(pyridin-2-yl)-4H-1,2,4-triazole-κ2 N 1,N 5]diaqua­cobalt(II) bis­(perchlorate)

Mi Feng; Yu-Fei Ji; Sheng-Li Liang; Zhi-Liang Liu

doi:10.1107/S1600536812038573

. 2012 Sep 15;68(Pt 10):m1272–m1273. doi: 10.1107/S1600536812038573

Bis[4-amino-3,5-bis(pyridin-2-yl)-4H-1,2,4-triazole-κ² N ¹,N ⁵]diaquacobalt(II) bis(perchlorate)

Mi Feng ^a, Yu-Fei Ji ^a, Sheng-Li Liang ^a, Zhi-Liang Liu ^a,^*

PMCID: PMC3470152 PMID: 23125596

Abstract

In the title structure, [Co(C₁₂H₁₀N₆)₂(H₂O)₂](ClO₄)₂, the Co^II atom lies on an inversion centre and is coordinated in a slightly distorted octahedral geometry by four N atoms from two 4-amino-3,5-bis(pyridin-2-yl)-4H-1,2,4-triazole (adpt) ligands in equatorial positions and two O atoms from two water molecules in axial positions. An intramolecular N—H⋯N interaction stabilizes the molecular conformation. Intermolecular N—H⋯O and O—H⋯O interactions involving the perchlorate counter-anions extend the monomeric compound into a two-dimensional network parallel to the bc plane.

Related literature

For the synthesis of the adpt ligand, see: Geldard & Lions (1965 ▶). For background to the coordination chemistry of the adpt ligand, see: Meng et al. (2009 ▶). For intramolecular hydrogen bonds in the adpt ligand, see: Kitchen et al. (2008 ▶). For other Co(II) coordination compounds with the same ligand, see: Keij et al. (1984 ▶); Peng et al. (2006 ▶); García-Couceiro et al. (2009 ▶); White et al. (2010 ▶).

Experimental

Crystal data

[Co(C₁₂H₁₀N₆)₂(H₂O)₂](ClO₄)₂
M _r = 770.38
Monoclinic,
a = 8.5839 (17) Å
b = 12.950 (3) Å
c = 14.975 (5) Å
β = 114.34 (2)°
V = 1516.7 (7) Å³
Z = 2
Mo Kα radiation
μ = 0.82 mm⁻¹
T = 293 K
0.04 × 0.03 × 0.01 mm

Data collection

Bruker SMART APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.971, T _max = 0.992
10155 measured reflections
2681 independent reflections
2336 reflections with I > 2σ(I)
R _int = 0.038

Refinement

R[F ² > 2σ(F ²)] = 0.050
wR(F ²) = 0.121
S = 1.07
2681 reflections
223 parameters
H-atom parameters constrained
Δρ_max = 0.87 e Å⁻³
Δρ_min = −0.50 e Å⁻³

Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT (Bruker, 2001 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg & Putz, 2006 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812038573/wm2664sup1.cif

e-68-m1272-sup1.cif^{(25.3KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812038573/wm2664Isup2.hkl

e-68-m1272-Isup2.hkl^{(131.7KB, 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
N6—H6B⋯N5	0.89	2.29	2.897 (4)	125
N6—H6B⋯O3ⁱ	0.89	2.39	2.989 (4)	124
O1—H1A⋯O4	0.85	2.16	2.782 (4)	130
O1—H1B⋯O2ⁱⁱ	0.85	2.22	2.983 (4)	150
O1—H1B⋯O5ⁱⁱ	0.85	2.58	3.284 (5)	141

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

Acknowledgments

We thank the NSFC (21061009) and the National Students of Innovation and Entrepreneurship Training Programs (111012608) for their financial support.

supplementary crystallographic information

Comment

Recently, 4-amine-3,5-di-2-pyridyl-1,2,4-triazol (adpt) has been used as a potential multidentate ligand to generate novel metal-organic complexes due to containing five N coordination sites and three potentially conjugated aromatic rings (Meng et al., 2009). Such complexes with adpt have interesting properties for potential applications in the fields of magnetic materials (Keij et al., 1984). Several Co(II) compounds containing adpt have been reported previously (Keij et al., 1984; Peng et al., 2006; García-Couceiro et al., 2009; White et al., 2010). Herein, the synthesis and crystal structure of the title complex [Co(C₁₂H₁₀N₆)₂(H₂O)₂](ClO₄)₂, (I), is reported.

As shown in Figure 1, compound (I) consists of one Co(II) atom located on an inversion centre, two adpt ligands, two water molecules and two isolated perchlorate counter anions. The Co(II) is six-coordinated by four N atoms from two adpt ligands and two O atoms from two water molecules, giving a slightly distorted octahedral coordination environment. The equatorial plane is defined by four N atoms from two adpt ligands with a chelate formation, and the axial positions are occupied by two O atoms of water molecules. The dihedral angle between the non-coordinated pyridine ring and the coordinating pyridine ring is 11.94 (16) ° and that between the coordinating pyridine ring and the triazole ring is 6.76 (6)°. In the mononuclear unit, an intramolecular N—H···N hydrogen-bonding interaction between the NH₂ group attached to the the triazole ring and the non-coordinating N atom of pyridine is observed (Kitchen et al., 2008). Intermolecular N—H···O and O—H···O hydrogen-bonding interactions exist between the amine group and the coordinating water molecules, respectively, with the O atoms of the isolated perchlorate counter anions. In the crystal, the molecular entities are linked by O—H···O hydrogen bonds generating chains along the b axis. These chains in turn aggregate into a two-dimensional network parallel to the bc plane (Fig. 2).

Experimental

4-Amino-3,5-bis(pyridin-2-yl)-4H-1,2,4-triazole (abpt, 5mmol) was dissolved in 20 ml mixture solution of water and methanol (1:1, v/v). Then Co(ClO₄)_2`4H₂O (5 mmol) was added to the above solution. The resulting solution was stirred for 3 h at room temperature. Upon slow evaporation of the solvent, dark red block-shaped crystals formed from the filtrate in a few days. The used 4-amine-3,5-di-2-pyridyl-1,2,4-triazol (adpt) was synthesized according to the previously reported procedure (Geldard & Lions, 1965).