Bis(μ-3,5-dimethyl-1,2,4-triazol-4-amine-κ2 N 1:N 2)bis­[dichlorido­cobalt(II)]

Yun Gong; Jinghua Li; Yuchao Zhou; Jianbo Qin; Xiaoxia Wu

doi:10.1107/S1600536809021916

. 2009 Jun 17;65(Pt 7):m791. doi: 10.1107/S1600536809021916

Bis(μ-3,5-dimethyl-1,2,4-triazol-4-amine-κ² N ¹:N ²)bis[dichloridocobalt(II)]

Yun Gong ^a,^*, Jinghua Li ^b, Yuchao Zhou ^a, Jianbo Qin ^a, Xiaoxia Wu ^b

PMCID: PMC2969463 PMID: 21582718

Abstract

In the centrosymmetric dinuclear compound, [Co₂Cl₄(C₄H₈N₄)₂], the Co^II atom is coordinated by N atoms from two 3,5-dimethyl-1,2,4-triazol-4-amine ligands and two Cl atoms in a distorted tetrahedral geometry. A six-membered ring is formed by four N atoms from two ligands and the two Co^II centers; the Co⋯Co distance is 3.756 (9) Å.

Related literature

For related compounds, see: Cheng et al. (2007 ▶); Lavrenova et al. (1992 ▶); Liu et al. (2003 ▶); Nockemann & Meyer (2007 ▶).

Experimental

Crystal data

[Co₂Cl₄(C₄H₈N₄)₂]
M _r = 483.95
Monoclinic,
a = 6.7412 (10) Å
b = 12.2094 (16) Å
c = 11.4423 (14) Å
β = 97.8270 (10)°
V = 933.0 (2) Å³
Z = 2
Mo Kα radiation
μ = 2.36 mm⁻¹
T = 298 K
0.34 × 0.33 × 0.17 mm

Data collection

Siemens SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.46, T _max = 0.67
4733 measured reflections
1638 independent reflections
1304 reflections with I > 2σ(I)
R _int = 0.023

Refinement

R[F ² > 2σ(F ²)] = 0.032
wR(F ²) = 0.085
S = 1.07
1638 reflections
102 parameters
H-atom parameters constrained
Δρ_max = 0.43 e Å⁻³
Δρ_min = −0.58 e Å⁻³

Data collection: SMART (Siemens, 1996 ▶); cell refinement: SAINT (Siemens, 1996 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 20008); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809021916/ng2584sup1.cif

e-65-0m791-sup1.cif^{(14KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809021916/ng2584Isup2.hkl

e-65-0m791-Isup2.hkl^{(80.7KB, hkl)}

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

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

Co1—N2ⁱ	2.023 (3)
Co1—N1	2.030 (3)
Co1—Cl2	2.2154 (11)
Co1—Cl1	2.2382 (11)

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N2ⁱ—Co1—N1	107.55 (11)
N2ⁱ—Co1—Cl2	108.46 (9)
N1—Co1—Cl2	108.50 (9)
N2ⁱ—Co1—Cl1	109.60 (9)
N1—Co1—Cl1	109.49 (9)
Cl2—Co1—Cl1	113.10 (5)

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Symmetry code: (i) Inline graphic .

Acknowledgments

This work was supported by the Natural Science Young Scholars Foundation of Chongqing University, the Large-scale Instrument and Equipment Open Foundation of Chongqing University, the Scientific Research Start-up Foundation of Chongqing University and Chongqing University Postgraduate Science and Innovation Fund.

supplementary crystallographic information

Comment

The rational design and synthesis of novel coordination polymers is of current interest in the field of supramolecular chemistry and crystal engineering, not only because of their intriguing structural motifs but also because of their potential applications in catalysis, molecular adsorption, magnetism, nonlinear optics, and molecular sensing. 1,2,4-Triazole and its derivatives possess good coordination ability due to the hetercyclic nitrogen atoms in the structure. Many polymers of 3,5-dimethyl-1,2,4-triazol-4-amine (Dmatrz) have been synthesized. In 1992, Lavrenova reported a series of metal-Dmatrz complexes, such as CuCl₂(Dmatrz)(0.5H₂O), CdCl₂(Dmatrz), Co(NO₃)₂(Dmatrz)₂(H₂O), Cu(NO₃)₂(Dmatrz)(0.5H₂O), Ni(NO₃)₂(Dmatrz)₂(H₂O), Zn(NO₃)₂(Dmatrz)₂, Cd(NO₃)₂(Dmatrz)₃ (Lavrenova et al., 1992). Other metal- Dmatrz complexes such as Cu(Dmatrz)SCN, Zn₂(Dmatrz)₂Cl₄, Ag₃(Dmatrz)₂(NO₃)₃ have also reported (Liu, et al., 2003; Cheng, et al., 2007; Nockemann, et al., 2007). However, so far coordination polymer constructed from CoCl₂ and Dmatrz has never been reported. In the present word, we solvothermally synthesized a CoCl₂-Dmatrz complex and it is reported here.

The molecular structure of the complex (I) (Fig. 1) has one one Co(II), one Dmatrz and two chlorine anions in its asymmetric unit. The Co(II) center is four-coordinated by four nitrogen atoms from two Dmatrz ligands and two chlorine atoms in a tetrahedral geometry. Each Dmatrz ligand links two Co(II) centers via its two neighboring nitrogen atoms with a Co···Co separation of 3.756 (9) Å (Fig.1). A six membered ring is formed via four nitrogen atoms from two Dmatrz ligands and two cobalt centers. The chlorine atoms can form hydrogen bonds with nitrogen atom from the uncoordinated amino group of Dmatrz. For example, The H4B···Cl2(ii) and N4···Cl2(ii) distances are 2.514 and 3.277 Å, respectively [Symmetry codes: (ii) -x + 1,-y,-z + 1]. The N4—H4B··· Cl2(ii) angle is 148.39 °.

Experimental

A mixture of Dmatrz(0.05 mmol, 0.006 g), CoCl₂(0.1 mmol, 0.024 g) and ethanol(5 mm l) was put into a Teflon-lined autoclave. The reaction mixture was heated at 120 centigrade for one and a half day, followed by slow cooling to room temperatrue and blue single crystals were collected. Elemental analyse found: C, 19.80; H, 3.39; N, 23.04; Cl, 29.28; Co, 24.45%.