Acta Cryst. (2009). E65, m791 [ doi:10.1107/S1600536809021916 ]
![[mu]](/logos/entities/mu_rmgif.gif)
-3,5-dimethyl-1,2,4-triazol-4-amine-![[kappa]](/logos/entities/kappa_rmgif.gif)
2N1:N2)bis[dichloridocobalt(II)]In the centrosymmetric dinuclear compound, [Co2Cl4(C4H8N4)2], the CoII 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 CoII centers; the Co
Co distance is 3.756 (9) Å.
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%.
H atoms were positioned geometrically and refined as riding atoms, with C—H = 0.96Å and Uiso(H) = 1.5Ueq(C) for methyl H atoms, N—H = 0.86Å and Uiso(H) = 1.2Ueq(C) for amino H atoms.
Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT (Siemens, 1996); 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 (Sheldrick, 2008).
![[Figure 1]](./ng2584fig1thm.gif)
| Fig. 1. The structure of (I), with the atomic numbering scheme and displacement ellipsoids at the 30% probability level. [Symmetry codes: (i) -x + 1,-y,-z + 1.] |
![[Figure 2]](./ng2584fig2thm.gif)
| Fig. 2. Three dimensional supramolecular architecture constructed by intermolecular hydrogen bonds. The dotted lines indicate the hydrogen bonds. |
| [Co2Cl4(C4H8N4)2] | F(000) = 484 |
| Mr = 483.95 | Dx = 1.723 Mg m−3 |
| Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -P 2ybc | Cell parameters from 4733 reflections |
| a = 6.7412 (10) Å | θ = 2.5–25.0° |
| b = 12.2094 (16) Å | µ = 2.36 mm−1 |
| c = 11.4423 (14) Å | T = 298 K |
| β = 97.827 (1)° | Block, blue |
| V = 933.0 (2) Å3 | 0.34 × 0.33 × 0.17 mm |
| Z = 2 |
| Siemens CCD area-detector diffractometer | 1638 independent reflections |
| Radiation source: fine-focus sealed tube | 1304 reflections with I > 2σ(I) |
| graphite | Rint = 0.023 |
| φ and ω scans | θmax = 25.0°, θmin = 2.5° |
| Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −7→7 |
| Tmin = 0.46, Tmax = 0.67 | k = −14→14 |
| 4733 measured reflections | l = −13→8 |
| Refinement on F2 | Primary atom site location: structure-invariant direct methods |
| Least-squares matrix: full | Secondary atom site location: difference Fourier map |
| R[F2 > 2σ(F2)] = 0.032 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.085 | H-atom parameters constrained |
| S = 1.07 | w = 1/[σ2(Fo2) + (0.0358P)2 + 1.1376P] where P = (Fo2 + 2Fc2)/3 |
| 1638 reflections | (Δ/σ)max = 0.001 |
| 102 parameters | Δρmax = 0.43 e Å−3 |
| 0 restraints | Δρmin = −0.58 e Å−3 |
| [Co2Cl4(C4H8N4)2] | V = 933.0 (2) Å3 |
| Mr = 483.95 | Z = 2 |
| Monoclinic, P21/c | Mo Kα radiation |
| a = 6.7412 (10) Å | µ = 2.36 mm−1 |
| b = 12.2094 (16) Å | T = 298 K |
| c = 11.4423 (14) Å | 0.34 × 0.33 × 0.17 mm |
| β = 97.827 (1)° |
| Siemens CCD area-detector diffractometer | 1638 independent reflections |
| Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1304 reflections with I > 2σ(I) |
| Tmin = 0.46, Tmax = 0.67 | Rint = 0.023 |
| 4733 measured reflections | θmax = 25.0° |
| R[F2 > 2σ(F2)] = 0.032 | H-atom parameters constrained |
| wR(F2) = 0.085 | Δρmax = 0.43 e Å−3 |
| S = 1.07 | Δρmin = −0.58 e Å−3 |
| 1638 reflections | Absolute structure: ? |
| 102 parameters | Flack parameter: ? |
| 0 restraints | Rogers parameter: ? |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
| x | y | z | Uiso*/Ueq | ||
| Co1 | 0.59569 (7) | 0.10736 (4) | 0.40423 (4) | 0.03186 (17) | |
| Cl1 | 0.84618 (15) | 0.10010 (9) | 0.29461 (10) | 0.0545 (3) | |
| Cl2 | 0.44352 (17) | 0.26855 (9) | 0.39618 (12) | 0.0652 (3) | |
| N1 | 0.7034 (4) | 0.0747 (2) | 0.5750 (2) | 0.0360 (7) | |
| N2 | 0.6098 (4) | 0.0089 (2) | 0.6507 (2) | 0.0345 (7) | |
| N3 | 0.8558 (4) | 0.0937 (2) | 0.7526 (2) | 0.0341 (7) | |
| N4 | 0.9948 (5) | 0.1233 (3) | 0.8494 (3) | 0.0505 (9) | |
| H4A | 0.9879 | 0.0948 | 0.9174 | 0.061* | |
| H4B | 1.0872 | 0.1700 | 0.8409 | 0.061* | |
| C1 | 0.7059 (5) | 0.0212 (3) | 0.7575 (3) | 0.0328 (8) | |
| C2 | 0.8540 (5) | 0.1240 (3) | 0.6382 (3) | 0.0365 (8) | |
| C3 | 0.6643 (6) | −0.0339 (3) | 0.8663 (3) | 0.0476 (10) | |
| H3A | 0.6222 | 0.0194 | 0.9195 | 0.071* | |
| H3B | 0.7834 | −0.0698 | 0.9030 | 0.071* | |
| H3C | 0.5602 | −0.0871 | 0.8471 | 0.071* | |
| C4 | 1.0012 (7) | 0.1982 (4) | 0.5962 (4) | 0.0576 (12) | |
| H4C | 1.0375 | 0.1709 | 0.5233 | 0.086* | |
| H4D | 1.1183 | 0.2022 | 0.6541 | 0.086* | |
| H4E | 0.9437 | 0.2699 | 0.5837 | 0.086* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Co1 | 0.0308 (3) | 0.0312 (3) | 0.0334 (3) | −0.00153 (19) | 0.00350 (19) | 0.0033 (2) |
| Cl1 | 0.0476 (6) | 0.0600 (6) | 0.0604 (6) | −0.0015 (5) | 0.0239 (5) | −0.0066 (5) |
| Cl2 | 0.0540 (7) | 0.0417 (6) | 0.0976 (9) | 0.0137 (5) | 0.0018 (6) | 0.0003 (6) |
| N1 | 0.0369 (17) | 0.0385 (16) | 0.0317 (16) | −0.0077 (13) | 0.0015 (13) | 0.0046 (13) |
| N2 | 0.0335 (16) | 0.0330 (15) | 0.0364 (16) | −0.0055 (12) | 0.0026 (13) | 0.0025 (13) |
| N3 | 0.0354 (16) | 0.0355 (16) | 0.0301 (15) | −0.0018 (13) | −0.0004 (12) | −0.0044 (12) |
| N4 | 0.051 (2) | 0.067 (2) | 0.0298 (16) | −0.0194 (17) | −0.0085 (14) | −0.0041 (15) |
| C1 | 0.0337 (19) | 0.0314 (18) | 0.0329 (19) | 0.0008 (15) | 0.0026 (14) | −0.0022 (14) |
| C2 | 0.0371 (19) | 0.0365 (19) | 0.0353 (19) | −0.0045 (15) | 0.0030 (15) | 0.0000 (15) |
| C3 | 0.058 (3) | 0.049 (2) | 0.036 (2) | −0.0039 (19) | 0.0052 (18) | 0.0071 (17) |
| C4 | 0.061 (3) | 0.067 (3) | 0.045 (2) | −0.029 (2) | 0.007 (2) | 0.000 (2) |
| Co1—N2i | 2.023 (3) | N4—H4A | 0.8600 |
| Co1—N1 | 2.030 (3) | N4—H4B | 0.8600 |
| Co1—Cl2 | 2.2154 (11) | C1—C3 | 1.475 (5) |
| Co1—Cl1 | 2.2382 (11) | C2—C4 | 1.472 (5) |
| N1—C2 | 1.310 (4) | C3—H3A | 0.9600 |
| N1—N2 | 1.394 (4) | C3—H3B | 0.9600 |
| N2—C1 | 1.312 (4) | C3—H3C | 0.9600 |
| N2—Co1i | 2.023 (3) | C4—H4C | 0.9600 |
| N3—C1 | 1.350 (4) | C4—H4D | 0.9600 |
| N3—C2 | 1.358 (4) | C4—H4E | 0.9600 |
| N3—N4 | 1.397 (4) | ||
| N2i—Co1—N1 | 107.55 (11) | N2—C1—N3 | 108.3 (3) |
| N2i—Co1—Cl2 | 108.46 (9) | N2—C1—C3 | 127.4 (3) |
| N1—Co1—Cl2 | 108.50 (9) | N3—C1—C3 | 124.3 (3) |
| N2i—Co1—Cl1 | 109.60 (9) | N1—C2—N3 | 108.1 (3) |
| N1—Co1—Cl1 | 109.49 (9) | N1—C2—C4 | 127.5 (3) |
| Cl2—Co1—Cl1 | 113.10 (5) | N3—C2—C4 | 124.4 (3) |
| C2—N1—N2 | 107.7 (3) | C1—C3—H3A | 109.5 |
| C2—N1—Co1 | 126.2 (2) | C1—C3—H3B | 109.5 |
| N2—N1—Co1 | 125.3 (2) | H3A—C3—H3B | 109.5 |
| C1—N2—N1 | 107.7 (3) | C1—C3—H3C | 109.5 |
| C1—N2—Co1i | 126.9 (2) | H3A—C3—H3C | 109.5 |
| N1—N2—Co1i | 124.1 (2) | H3B—C3—H3C | 109.5 |
| C1—N3—C2 | 108.1 (3) | C2—C4—H4C | 109.5 |
| C1—N3—N4 | 124.1 (3) | C2—C4—H4D | 109.5 |
| C2—N3—N4 | 127.6 (3) | H4C—C4—H4D | 109.5 |
| N3—N4—H4A | 120.0 | C2—C4—H4E | 109.5 |
| N3—N4—H4B | 120.0 | H4C—C4—H4E | 109.5 |
| H4A—N4—H4B | 120.0 | H4D—C4—H4E | 109.5 |
| Symmetry codes: (i) −x+1, −y, −z+1. |
| Co1—N2i | 2.023 (3) | Co1—Cl2 | 2.2154 (11) |
| Co1—N1 | 2.030 (3) | Co1—Cl1 | 2.2382 (11) |
| N2i—Co1—N1 | 107.55 (11) | N2i—Co1—Cl1 | 109.60 (9) |
| N2i—Co1—Cl2 | 108.46 (9) | N1—Co1—Cl1 | 109.49 (9) |
| N1—Co1—Cl2 | 108.50 (9) | Cl2—Co1—Cl1 | 113.10 (5) |
| Symmetry codes: (i) −x+1, −y, −z+1. |
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.
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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 °.