Diaqua­bis­[2,6-bis­(4H-1,2,4-triazol-4-yl)pyridine-κN 2]bis­(seleno­cyanato-κN)cobalt(II)

Yuan-Yuan Liu; Pan Yang

doi:10.1107/S1600536812032461

. 2012 Jul 21;68(Pt 8):m1097–m1098. doi: 10.1107/S1600536812032461

Diaquabis[2,6-bis(4H-1,2,4-triazol-4-yl)pyridine-κN ²]bis(selenocyanato-κN)cobalt(II)

Yuan-Yuan Liu ^a,^*, Pan Yang ^a

PMCID: PMC3414148 PMID: 22904755

Abstract

In the title compound, [Co(NCSe)₂(C₉H₇N₇)₂(H₂O)₂], the Co²⁺ cation is coordinated by two selenocyanate anions, two 2,6-bis(4H-1,2,4-triazol-4-yl)pyridine ligands and two water molecules within a slightly distorted N₄O₂ octahedron. The asymmetric unit consists of one Co²⁺ cation, which is located on a center of inversion, as well as one selenocyanate anion, one 2,6-bis(4H-1,2,4-triazol-4-yl)pyridine ligand and one water molecule in general positions. Intermolecular O—H⋯N hydrogen bonds join the complex molecules into layers parallel to the bc plane. The layers are linked by C—H⋯N and C—H⋯Se hydrogen bonds into a three-dimensional supramolecular architecture.

Related literature

For general background to this work, see: Liu et al. (2007 ▶). Previous research on compounds with Co(II) as cation have found a slow relaxation of the magnetization, see: Boeckmann & Näther (2010, ▶ 2011 ▶, 2012) ▶. For related structures, see: Du et al. (2009 ▶); Yang et al. (2008 ▶).

Experimental

Crystal data

[Co(NCSe)₂(C₉H₇N₇)₂(H₂O)₂]
M _r = 731.35
Monoclinic,
a = 17.5460 (16) Å
b = 7.2752 (7) Å
c = 20.3148 (19) Å
β = 95.691 (2)°
V = 2580.4 (4) Å³
Z = 4
Mo Kα radiation
μ = 3.54 mm⁻¹
T = 173 K
0.15 × 0.14 × 0.13 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.619, T _max = 0.656
6336 measured reflections
2280 independent reflections
2083 reflections with I > 2σ(I)
R _int = 0.026

Refinement

R[F ² > 2σ(F ²)] = 0.026
wR(F ²) = 0.065
S = 1.05
2280 reflections
186 parameters
H-atom parameters constrained
Δρ_max = 0.59 e Å⁻³
Δρ_min = −0.58 e Å⁻³

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL and DIAMOND (Brandenburg, 1999 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812032461/zj2088sup1.cif

e-68-m1097-sup1.cif^{(18.8KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812032461/zj2088Isup2.hkl

e-68-m1097-Isup2.hkl^{(112.2KB, hkl)}

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

Table 1. Selected bond lengths (Å).

Co1—N8	2.097 (2)
Co1—N3	2.122 (2)
Co1—O1	2.1434 (18)

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1A⋯N2	0.84	2.43	3.017 (3)	127
O1—H1B⋯N7ⁱⁱ	0.84	2.00	2.837 (3)	173
C1—H1⋯N6ⁱⁱⁱ	0.95	2.37	3.293 (3)	163
C5—H5⋯N8^iv	0.95	2.56	3.356 (3)	142
C7—H7⋯N6ⁱⁱⁱ	0.95	2.46	3.373 (3)	162
C9—H9⋯Se1^iv	0.95	2.96	3.877 (3)	164

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

Acknowledgments

This work was supported financially by Tianjin Educational Committee (20090504, 20110301) and Tianjin Normal University (1E0402B).

supplementary crystallographic information

Comment

Previously we have reported on the a series of novel zinc(II) and cadmium(II) compounds based on 2,6-di-(1,2,4-triazole-4-yl)pyridine (Liu et al., 2007). On the other hand, dependent on the nature of the metal cation, anti- or ferromagnetic ordering is observed and for the compounds with Co(II) as cation preivous resrarch have found a slow relaxation of the magnetization (Boeckmann & Näther 2010, 2011, 2012). To investigate the influence of the co-ligand on the magnetic properties for the compounds with Co(II), we tried to prepare cobalt(II) compounds based on 2,6-di-(1,2,4-triazole-4-yl)pyridine, which resulted in the formation of the title compound in which the neutral ligands are only terminal N-coordinated. This compound was characterized only by single-crystal X-ray diffraction. In the crystal structure the cobalt(II) cations are coordinated by four nitrogen atoms of two terminal N-bonded seleno-cyanato anions and two terminal bonded 2,6-di-(1,2,4-triazole-4-yl)pyridine co-ligands as well as two water molecules into discrete complexes (Fig. 1). The coordination polyhedron of the Co cations can be described as a slightly distorted octahedron with the Co cation located on a centre of inversion. The discrete cobalt complexes are bridged by intermolecular O—H···N, C—H···N and C—H···Se hydrogen bonds (Yang et al., 2008; Du et al., 2009), wich assemble (I) into a three-dimensional supra-molecular architecture(Fig. 2 and Table 1).

Perspective drawing with the atomic numbering scheme is illustrated in figure 1. Selected geometric parameters (Å, °) for (I) are listed in table 1. Selected hydrogen-bonding geometric parameters (Å, °) for (I) are listed in table 2. The two-dimensional supramolecular framework of (I) is shown in Figure 2.

Experimental

The compound was synthesized under hydrothermal conditions. A mixture of L (L = 1,4-Bis(2,6-Bis(4H-1,2,4-triazol-4-yl)pyridine) (0.3 mmol, 0.0636 g), CoSO₄.7H₂O (0.1 mmol, 0.028 g), KSeCN (0.2 mmol, 0.029 g) and water (10 ml) was placed in a 25 ml acid digestion bomb and heated at 393 K for two days, then equably cooled to room temperature for three days. After washed by 5 ml water for twice, Red block crystals of the compound were obtained..