Acta Cryst. (2007). E63, m1591 [ doi:10.1107/S1600536807021393 ]
In the title complex, [Co(C5H3N3)2(H2O)2], prepared in a one-pot synthesis, the CoII atom (site symmetry 
), is coordinated by four N atoms from two 5-(2-pyrazinyl)tetrazolate ligands and by two water molecules in a distorted trans-CoO2N4 octahedral geometry. A supramolecular network is formed via intermolecular O-H
N hydrogen bonds.
Hydrothermal treatment of CoCl2.6H2O (1.0 mmol, 0.237 g), 2-cyanopyrazine (1 mmol, 0.105 g), NaN3 (1 mmol, 0.065 g), and water (3 ml) over 50 h at 422 K yielded red prisms of (I) (yield 78%).
The water H atoms were located in a difference Fourier map and their positions were freely refined with Uiso(H) = 1.2Ueq(O). The other H atoms were placed
in calculated positions (C—H = 0.93 Å) refined using a riding model with Uiso(H) = 1.2Ueq(C).
Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2004); software used to prepare material for publication: SHELXTL.
![[Figure 1]](./hb2381fig1thm.gif)
| Fig. 1. The structure of (I), showing the atomic numbering scheme. Non-H atoms are shown as 50% probability displacement ellipsoids. Unlabelled atoms are related to the labelled atoms by the symmetry operator (1 - x, 1 - y, -z). |
![[Figure 2]](./hb2381fig2thm.gif)
| Fig. 2. A packing diagram of (I). Hydrogen bonds are depicted as broken lines. |
| [Co(C5H3N3)2(H2O)2] | F(000) = 394 |
| Mr = 389.23 | Dx = 1.809 Mg m−3 |
| Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -P 2yn | Cell parameters from 5700 reflections |
| a = 6.0676 (1) Å | θ = 1.7–28.0° |
| b = 11.4221 (2) Å | µ = 1.24 mm−1 |
| c = 10.7096 (2) Å | T = 293 K |
| β = 105.652 (1)° | Prism, red |
| V = 714.70 (2) Å3 | 0.18 × 0.16 × 0.15 mm |
| Z = 2 |
| Bruker APEXII area-detector diffractometer | 1693 independent reflections |
| Radiation source: fine-focus sealed tube | 1325 reflections with I > 2σ(I) |
| graphite | Rint = 0.035 |
| φ and ω scans | θmax = 27.9°, θmin = 2.7° |
| Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −7→7 |
| Tmin = 0.808, Tmax = 0.836 | k = −15→14 |
| 6011 measured reflections | l = −14→12 |
| 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)] = 0.034 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.083 | H atoms treated by a mixture of independent and constrained refinement |
| S = 1.06 | w = 1/[σ2(Fo2) + (0.0392P)2 + 0.1286P] where P = (Fo2 + 2Fc2)/3 |
| 1693 reflections | (Δ/σ)max < 0.001 |
| 121 parameters | Δρmax = 0.33 e Å−3 |
| 3 restraints | Δρmin = −0.30 e Å−3 |
| [Co(C5H3N3)2(H2O)2] | V = 714.70 (2) Å3 |
| Mr = 389.23 | Z = 2 |
| Monoclinic, P21/n | Mo Kα radiation |
| a = 6.0676 (1) Å | µ = 1.24 mm−1 |
| b = 11.4221 (2) Å | T = 293 K |
| c = 10.7096 (2) Å | 0.18 × 0.16 × 0.15 mm |
| β = 105.652 (1)° |
| Bruker APEXII area-detector diffractometer | 1693 independent reflections |
| Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1325 reflections with I > 2σ(I) |
| Tmin = 0.808, Tmax = 0.836 | Rint = 0.035 |
| 6011 measured reflections | θmax = 27.9° |
| R[F2 > 2σ(F2)] = 0.034 | H atoms treated by a mixture of independent and constrained refinement |
| wR(F2) = 0.083 | Δρmax = 0.33 e Å−3 |
| S = 1.06 | Δρmin = −0.30 e Å−3 |
| 1693 reflections | Absolute structure: ? |
| 121 parameters | Flack parameter: ? |
| 3 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 | ||
| C1 | 0.5209 (3) | 0.24786 (18) | 0.0722 (2) | 0.0292 (5) | |
| C2 | 0.4676 (4) | 0.13095 (19) | 0.0833 (3) | 0.0422 (6) | |
| H2 | 0.5804 | 0.0813 | 0.1314 | 0.051* | |
| C3 | 0.1084 (4) | 0.1622 (2) | −0.0407 (3) | 0.0437 (6) | |
| H3 | −0.0379 | 0.1351 | −0.0813 | 0.052* | |
| C4 | 0.1588 (4) | 0.2787 (2) | −0.0534 (2) | 0.0355 (5) | |
| H4 | 0.0459 | 0.3277 | −0.1025 | 0.043* | |
| C5 | 0.7458 (3) | 0.29806 (18) | 0.1328 (2) | 0.0292 (5) | |
| Co1 | 0.5000 | 0.5000 | 0.0000 | 0.02720 (14) | |
| H1W | 0.305 (3) | 0.5142 (18) | 0.182 (2) | 0.053* | |
| H2W | 0.457 (4) | 0.5988 (15) | 0.212 (2) | 0.053* | |
| N1 | 0.3655 (3) | 0.32279 (14) | 0.00284 (17) | 0.0286 (4) | |
| N2 | 0.2619 (3) | 0.08721 (18) | 0.0278 (2) | 0.0507 (6) | |
| N3 | 0.9254 (3) | 0.24591 (16) | 0.21020 (19) | 0.0355 (4) | |
| N4 | 1.0867 (3) | 0.32889 (18) | 0.2402 (2) | 0.0427 (5) | |
| N5 | 1.0062 (3) | 0.42684 (17) | 0.1815 (2) | 0.0393 (5) | |
| N6 | 0.7895 (3) | 0.41001 (15) | 0.11191 (18) | 0.0306 (4) | |
| O1W | 0.4169 (3) | 0.53856 (16) | 0.17002 (18) | 0.0428 (4) |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| C1 | 0.0287 (11) | 0.0243 (10) | 0.0337 (12) | 0.0012 (8) | 0.0066 (9) | 0.0007 (9) |
| C2 | 0.0394 (13) | 0.0269 (12) | 0.0563 (17) | 0.0021 (10) | 0.0057 (12) | 0.0062 (11) |
| C3 | 0.0346 (12) | 0.0398 (14) | 0.0532 (16) | −0.0101 (10) | 0.0061 (12) | −0.0053 (12) |
| C4 | 0.0295 (11) | 0.0368 (12) | 0.0378 (13) | −0.0004 (9) | 0.0053 (10) | −0.0005 (10) |
| C5 | 0.0292 (11) | 0.0241 (10) | 0.0343 (12) | 0.0034 (8) | 0.0086 (9) | 0.0032 (9) |
| Co1 | 0.0264 (2) | 0.0196 (2) | 0.0336 (2) | −0.00012 (16) | 0.00481 (16) | 0.00184 (17) |
| N1 | 0.0296 (9) | 0.0247 (9) | 0.0310 (10) | 0.0007 (7) | 0.0072 (8) | 0.0009 (7) |
| N2 | 0.0447 (12) | 0.0308 (11) | 0.0706 (16) | −0.0105 (9) | 0.0055 (11) | 0.0010 (11) |
| N3 | 0.0286 (9) | 0.0329 (10) | 0.0419 (11) | 0.0020 (8) | 0.0041 (8) | 0.0081 (9) |
| N4 | 0.0323 (10) | 0.0448 (12) | 0.0461 (12) | −0.0013 (9) | 0.0024 (9) | 0.0063 (10) |
| N5 | 0.0310 (10) | 0.0365 (11) | 0.0465 (12) | −0.0049 (8) | 0.0039 (9) | 0.0003 (9) |
| N6 | 0.0249 (9) | 0.0261 (9) | 0.0382 (11) | −0.0014 (7) | 0.0042 (8) | 0.0007 (8) |
| O1W | 0.0455 (10) | 0.0381 (9) | 0.0503 (11) | −0.0154 (8) | 0.0225 (9) | −0.0143 (8) |
| C1—N1 | 1.340 (2) | Co1—O1W | 2.0638 (18) |
| C1—C2 | 1.386 (3) | Co1—O1Wi | 2.0638 (18) |
| C1—C5 | 1.461 (3) | Co1—N6i | 2.1076 (17) |
| C2—N2 | 1.327 (3) | Co1—N6 | 2.1076 (17) |
| C2—H2 | 0.9300 | Co1—N1i | 2.1856 (16) |
| C3—N2 | 1.330 (3) | Co1—N1 | 2.1856 (16) |
| C3—C4 | 1.381 (3) | N3—N4 | 1.338 (3) |
| C3—H3 | 0.9300 | N4—N5 | 1.311 (3) |
| C4—N1 | 1.335 (3) | N5—N6 | 1.339 (2) |
| C4—H4 | 0.9300 | O1W—H1W | 0.777 (15) |
| C5—N3 | 1.320 (3) | O1W—H2W | 0.819 (15) |
| C5—N6 | 1.337 (3) | ||
| N1—C1—C2 | 121.15 (19) | O1Wi—Co1—N1i | 90.25 (7) |
| N1—C1—C5 | 115.39 (18) | N6i—Co1—N1i | 78.31 (6) |
| C2—C1—C5 | 123.46 (19) | N6—Co1—N1i | 101.69 (6) |
| N2—C2—C1 | 122.5 (2) | O1W—Co1—N1 | 90.25 (7) |
| N2—C2—H2 | 118.8 | O1Wi—Co1—N1 | 89.75 (7) |
| C1—C2—H2 | 118.8 | N6i—Co1—N1 | 101.69 (6) |
| N2—C3—C4 | 122.3 (2) | N6—Co1—N1 | 78.31 (6) |
| N2—C3—H3 | 118.9 | N1i—Co1—N1 | 180.0 |
| C4—C3—H3 | 118.9 | C4—N1—C1 | 116.36 (18) |
| N1—C4—C3 | 121.7 (2) | C4—N1—Co1 | 130.69 (15) |
| N1—C4—H4 | 119.2 | C1—N1—Co1 | 112.94 (13) |
| C3—C4—H4 | 119.2 | C2—N2—C3 | 116.0 (2) |
| N3—C5—N6 | 111.69 (19) | C5—N3—N4 | 104.92 (17) |
| N3—C5—C1 | 128.00 (19) | N5—N4—N3 | 109.61 (17) |
| N6—C5—C1 | 120.31 (18) | N4—N5—N6 | 109.10 (17) |
| O1W—Co1—O1Wi | 180.0 | C5—N6—N5 | 104.68 (17) |
| O1W—Co1—N6i | 91.90 (7) | C5—N6—Co1 | 112.91 (13) |
| O1Wi—Co1—N6i | 88.10 (7) | N5—N6—Co1 | 142.10 (14) |
| O1W—Co1—N6 | 88.10 (7) | Co1—O1W—H1W | 120.3 (18) |
| O1Wi—Co1—N6 | 91.90 (7) | Co1—O1W—H2W | 123.5 (16) |
| N6i—Co1—N6 | 180.0 | H1W—O1W—H2W | 111 (2) |
| O1W—Co1—N1i | 89.75 (7) |
| Symmetry codes: (i) −x+1, −y+1, −z. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O1W—H1W···N5ii | 0.78 (2) | 2.07 (2) | 2.832 (2) | 168 (2) |
| O1W—H2W···N3iii | 0.82 (2) | 1.93 (2) | 2.740 (2) | 171 (2) |
| Symmetry codes: (ii) x−1, y, z; (iii) −x+3/2, y+1/2, −z+1/2. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O1W—H1W···N5i | 0.78 (2) | 2.07 (2) | 2.832 (2) | 168 (2) |
| O1W—H2W···N3ii | 0.82 (2) | 1.93 (2) | 2.740 (2) | 171 (2) |
| Symmetry codes: (i) x−1, y, z; (ii) −x+3/2, y+1/2, −z+1/2. |
The authors acknowledge South China Normal University for supporting this work.
Bruker (2004). APEX2 (Version 6.12) and SMART (Version 6.12). Bruker AXS Inc., Madison, Wisconsin, USA.
Demko, Z. P. & Sharpless, K. B. (2001a). J. Org. Chem. 66, 7945–7950.
Demko, Z. P. & Sharpless, K. B. (2001b). Org. Lett. 3, 4091–4094.
Deng, H., Qiu, Y.-C., Zeng, R.-H. & Sun, F. (2007). Acta Cryst. E63, m450–m451.
Eddaoudi, M., Moler, D. B., Li, H. L., Chen, B. L., Reineke, T. M., O'Keeffe, M. & Yaghi, O. M. (2001). Acc. Chem. Res. 34, 319–330.
Rizk, A. T., Kilner, C. A. & Halcrow, M. A. (2005). CrystEngComm, 7, 359–362.
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.
Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.
The design, synthesis, characterization, and properties of supramolecular networks formed by using functionalized organic molecules as bridges between metal centers are of great interest (Rizk et al., 2005; Eddaoudi et al., 2001). The reports on tetrazoles is expanding rapidly, since tetrazoles have an important role in coordination chemistry as a ligand (Deng et al., 2006). Recently, 5-substituted 1H-tetrazoles have been synthesized by a facile approach (Demko & Sharpless, 2001a, 2001b). In the general reaction, the tetrazoles are prepared by the addition of azide to nitriles in water with the aid of a lewis acid such a Zn2+. In this paper, we selected 2-cyanopyrazine, NaN3 and a Lewis acid CoCl2 as reagent, to yield in one step the mononuclear structure (I) under hydrothermal condition.
In (I), the CoII atom, located on an inversion center, is coordinated by four N atoms from two 5-(2-pyrazinyl)tetrazolate ligands and two water molecules in a distorted octahedral geometry (Fig. 1; Table 1). In the ligand, the pyrazinyl and tetrazolyl rings are almost coplanar, with a dihedral angle of 3.53 (4)°. Intermolecular O—H···N hydrogen bonds (Table 2) form a supramolecular network (Fig. 2).