Acta Cryst. (2009). E65, m502 [ doi:10.1107/S1600536809012227 ]
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2-azido-3-pyrazine-2-carboxylato-cadmium(II)]The title compound, [Cd(C5H3N2O2)(N3)]n, has been prepared by the reaction of pyrazine-2-carboxylic acid, cadmium(II) nitrate and sodium azide. In the structure, the CdII atom is six-coordinated by two azide anions and three pyrazine-2-carboxylate ligands. Each pyrazine-2-carboxylate ligand bridges three CdII atoms, whereas the azide ligand bridges two CdII atoms, resulting in the formation of a two-dimensional metal-organic polymer developing parallel to the (100) plane.
A mixture of cadmium(II)nitrate and sodium azide (1 mmol), pyrazine-2-carboxylate acid(0.5 mmol), in 10 ml of water was sealed in a Teflon-lined stainless-steel Parr bomb that was heated at 363 K for 48 h. Pink crystals of the title complex were collected after the bomb was allowed to cool to room temperature.Yield 30% based on cadmium(II). Caution:Metal azides may be explosive. Although we have met no problems in this work, only a small amount of them should be prepared and handled with great caution.
Hydrogen atoms were included in calculated positions and treated as riding on their parent C atoms with C—H = 0.93Å and Uiso(H) = 1.2Ueq(C).
Data collection: SCXmini (Rigaku, 2006); cell refinement: PROCESS-AUTO (Rigaku, 1998); data reduction: PROCESS-AUTO (Rigaku, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPIII (Burnett & Johnson, 1996) and PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).
![[Figure 1]](./dn2435fig1thm.gif)
| Fig. 1. A view of the title compound showing the coordination of Cd atom with the atom-labelling scheme. Ellipsoids are drawn at the 50% probability level. H atom have been omitted for clarity. [Symmetry codes: (i) -x+1, y-1/2, -z+1/2; (ii) x, -y+1/2, z-1/2; (iii) -x+1, -y+1, -z+1; (iv) x, -y+1/2, z+1/2; (v) -x+1, y+1/2, -z+1/2] |
| [Cd(C5H3N2O2)(N3)] | F(000) = 528 |
| Mr = 277.52 | Dx = 2.424 Mg m−3 |
| Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -P 2ybc | Cell parameters from 7230 reflections |
| a = 11.857 (2) Å | θ = 3.1–27.5° |
| b = 9.839 (2) Å | µ = 2.84 mm−1 |
| c = 6.6250 (13) Å | T = 293 K |
| β = 100.33 (3)° | Block, yellow |
| V = 760.4 (3) Å3 | 0.2 × 0.18 × 0.15 mm |
| Z = 4 |
| Rigaku SCXmini diffractometer | 1741 independent reflections |
| Radiation source: fine-focus sealed tube | 1517 reflections with I > 2σ(I) |
| graphite | Rint = 0.067 |
| ω scans | θmax = 27.5°, θmin = 3.5° |
| Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | h = −15→15 |
| Tmin = 0.537, Tmax = 0.643 | k = −12→12 |
| 7718 measured reflections | l = −8→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)] = 0.046 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.117 | H-atom parameters constrained |
| S = 1.20 | w = 1/[σ2(Fo2) + (0.0408P)2 + 2.6851P] where P = (Fo2 + 2Fc2)/3 |
| 1741 reflections | (Δ/σ)max < 0.001 |
| 118 parameters | Δρmax = 0.74 e Å−3 |
| 0 restraints | Δρmin = −1.09 e Å−3 |
| [Cd(C5H3N2O2)(N3)] | V = 760.4 (3) Å3 |
| Mr = 277.52 | Z = 4 |
| Monoclinic, P21/c | Mo Kα radiation |
| a = 11.857 (2) Å | µ = 2.84 mm−1 |
| b = 9.839 (2) Å | T = 293 K |
| c = 6.6250 (13) Å | 0.2 × 0.18 × 0.15 mm |
| β = 100.33 (3)° |
| Rigaku SCXmini diffractometer | 1517 reflections with I > 2σ(I) |
| Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | Rint = 0.067 |
| Tmin = 0.537, Tmax = 0.643 | θmax = 27.5° |
| 7718 measured reflections | Standard reflections: 0 |
| 1741 independent reflections |
| R[F2 > 2σ(F2)] = 0.046 | H-atom parameters constrained |
| wR(F2) = 0.117 | Δρmax = 0.74 e Å−3 |
| S = 1.20 | Δρmin = −1.09 e Å−3 |
| 1741 reflections | Absolute structure: ? |
| 118 parameters | Flack parameter: ? |
| 0 restraints | Rogers parameter: ? |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 | ||
| Cd1 | 0.42263 (4) | 0.36045 (4) | 0.34194 (7) | 0.02481 (18) | |
| N1 | 0.3555 (5) | 0.1927 (5) | 0.5059 (8) | 0.0287 (12) | |
| N2 | 0.2937 (5) | 0.1135 (5) | 0.4006 (8) | 0.0248 (12) | |
| N3 | 0.2327 (6) | 0.0399 (7) | 0.3035 (10) | 0.0466 (17) | |
| N4 | 0.2558 (4) | 0.4910 (5) | 0.3100 (7) | 0.0231 (11) | |
| N5 | 0.0689 (5) | 0.6646 (7) | 0.1984 (10) | 0.0390 (15) | |
| O1 | 0.4718 (3) | 0.5816 (4) | 0.3145 (6) | 0.0197 (8) | |
| O2 | 0.4043 (4) | 0.7823 (4) | 0.1835 (6) | 0.0250 (9) | |
| C1 | 0.3913 (5) | 0.6650 (6) | 0.2480 (8) | 0.0198 (12) | |
| C2 | 0.2694 (5) | 0.6193 (6) | 0.2517 (8) | 0.0194 (12) | |
| C3 | 0.1769 (5) | 0.7052 (7) | 0.1982 (9) | 0.0277 (14) | |
| H3A | 0.1898 | 0.7942 | 0.1609 | 0.033* | |
| C4 | 0.0571 (6) | 0.5372 (9) | 0.2550 (11) | 0.0422 (19) | |
| H4A | −0.0162 | 0.5044 | 0.2575 | 0.051* | |
| C5 | 0.1493 (6) | 0.4509 (8) | 0.3106 (10) | 0.0327 (16) | |
| H5B | 0.1362 | 0.3623 | 0.3494 | 0.039* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Cd1 | 0.0233 (3) | 0.0213 (3) | 0.0287 (3) | −0.00024 (18) | 0.00174 (19) | 0.00118 (18) |
| N1 | 0.038 (3) | 0.023 (3) | 0.024 (3) | −0.008 (2) | 0.002 (2) | −0.001 (2) |
| N2 | 0.022 (3) | 0.025 (3) | 0.027 (3) | −0.003 (2) | 0.003 (2) | 0.000 (2) |
| N3 | 0.051 (4) | 0.047 (4) | 0.040 (3) | −0.023 (3) | 0.001 (3) | −0.004 (3) |
| N4 | 0.022 (3) | 0.025 (3) | 0.023 (2) | −0.004 (2) | 0.005 (2) | −0.003 (2) |
| N5 | 0.018 (3) | 0.054 (4) | 0.044 (3) | 0.002 (3) | 0.004 (3) | −0.008 (3) |
| O1 | 0.014 (2) | 0.020 (2) | 0.025 (2) | −0.0004 (16) | 0.0012 (16) | 0.0018 (17) |
| O2 | 0.023 (2) | 0.018 (2) | 0.033 (2) | −0.0007 (17) | 0.0035 (18) | 0.0075 (18) |
| C1 | 0.018 (3) | 0.026 (3) | 0.013 (3) | −0.004 (2) | 0.000 (2) | −0.001 (2) |
| C2 | 0.015 (3) | 0.028 (3) | 0.014 (2) | −0.001 (2) | −0.001 (2) | −0.002 (2) |
| C3 | 0.019 (3) | 0.031 (4) | 0.031 (3) | 0.000 (3) | −0.001 (3) | −0.001 (3) |
| C4 | 0.018 (4) | 0.071 (6) | 0.040 (4) | −0.012 (3) | 0.011 (3) | −0.010 (4) |
| C5 | 0.022 (3) | 0.043 (4) | 0.034 (4) | −0.016 (3) | 0.010 (3) | −0.003 (3) |
| Cd1—N1 | 2.202 (5) | N5—C4 | 1.324 (10) |
| Cd1—O2i | 2.226 (4) | N5—C3 | 1.342 (8) |
| Cd1—O1 | 2.268 (4) | O1—C1 | 1.275 (7) |
| Cd1—N4 | 2.336 (5) | O2—C1 | 1.250 (7) |
| Cd1—O1ii | 2.460 (4) | C1—C2 | 1.517 (8) |
| N1—N2 | 1.203 (7) | C2—C3 | 1.380 (8) |
| N1—Cd1iii | 2.286 (5) | C3—H3A | 0.9300 |
| N2—N3 | 1.138 (8) | C4—C5 | 1.381 (11) |
| N4—C5 | 1.324 (8) | C4—H4A | 0.9300 |
| N4—C2 | 1.339 (8) | C5—H5B | 0.9300 |
| N1—Cd1—O2i | 101.42 (19) | C2—N4—Cd1 | 113.6 (4) |
| N1—Cd1—O1 | 151.56 (18) | C4—N5—C3 | 115.6 (6) |
| O2i—Cd1—O1 | 94.12 (15) | C1—O1—Cd1 | 117.2 (4) |
| N1—Cd1—N1iv | 102.45 (15) | C1—O1—Cd1ii | 113.3 (3) |
| O2i—Cd1—N1iv | 90.68 (18) | Cd1—O1—Cd1ii | 104.11 (15) |
| O1—Cd1—N1iv | 101.01 (17) | C1—O2—Cd1v | 121.1 (4) |
| N1—Cd1—N4 | 94.7 (2) | O2—C1—O1 | 125.6 (5) |
| O2i—Cd1—N4 | 163.79 (17) | O2—C1—C2 | 117.0 (5) |
| O1—Cd1—N4 | 71.99 (16) | O1—C1—C2 | 117.4 (5) |
| N1iv—Cd1—N4 | 84.05 (18) | N4—C2—C3 | 121.3 (6) |
| N1—Cd1—O1ii | 83.47 (16) | N4—C2—C1 | 116.7 (5) |
| O2i—Cd1—O1ii | 80.03 (14) | C3—C2—C1 | 122.0 (5) |
| O1—Cd1—O1ii | 75.89 (15) | N5—C3—C2 | 122.2 (6) |
| N1iv—Cd1—O1ii | 169.88 (17) | N5—C3—H3A | 118.9 |
| N4—Cd1—O1ii | 103.82 (15) | C2—C3—H3A | 118.9 |
| N2—N1—Cd1 | 115.8 (4) | N5—C4—C5 | 122.6 (6) |
| N2—N1—Cd1iii | 119.1 (4) | N5—C4—H4A | 118.7 |
| Cd1—N1—Cd1iii | 124.0 (2) | C5—C4—H4A | 118.7 |
| N3—N2—N1 | 178.0 (7) | N4—C5—C4 | 121.7 (7) |
| C5—N4—C2 | 116.6 (6) | N4—C5—H5B | 119.1 |
| C5—N4—Cd1 | 128.9 (5) | C4—C5—H5B | 119.1 |
| Symmetry codes: (i) −x+1, y−1/2, −z+1/2; (ii) −x+1, −y+1, −z+1; (iii) x, −y+1/2, z+1/2; (iv) x, −y+1/2, z−1/2; (v) −x+1, y+1/2, −z+1/2. |
Burnett, M. N. & Johnson, C. K. (1996). ORTEPIII. Report ORNL-6895. Oak Ridge National Laboratory, Tennessee, USA.
Escuer, A., Vicente, R., Mautner, F. A. & Goher, M. A. S. (1997). Inorg. Chem. 36, 1233–1236.
Gu, Z.-G., Song, Y., Zuo, J.-L. & You, X.-Z. (2007). Inorg. Chem. 46, 9522–9524.
Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan.
Liu, F.-C., Zeng, Y.-F., Li, J.-R., Bu, X.-H., Zhang, H.-J. & Ribas, J. (2005). Inorg. Chem. 44, 7298–7300.
Mondal, K.-C. & Mukherjee, P.-S. (2008). Inorg. Chem. 47, 4215–4225.
Monfort, M., Resino, I., Ribas, J. & Stoeckli-Evans, H. (2000). Angew. Chem. Int. Ed. 39, 191–193.
Rigaku (1998). PROCESS-AUTO. Rigaku Corporation, Tokyo, Japan.
Rigaku (2006). SCXmini. Rigaku Americas Corporation, The Woodlands, Texas, USA.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Shen, Z., Zuo, J.-L., Gao, S., Song, Y., Che, C.-M., Fun, H.-K. & You, X.-Z. (2000). Angew. Chem. Int. Ed. 39, 3633–3635.
Spek, A. L. (2009). Acta Cryst. D65, 148–155.
Recently, metal azide complexes have attracted great attention.(Mondal & Mukherjee, 2008; Gu et al., 2007). The azide anion have rich coordinated modes. (Shen,et al., 2000). In this sense, lots metal-azide complexes have been reported.(Monfort,et al., 2000). In most of the compounds reported to date, the coligands are neutral organic ligands, while charged ligands are very scarce (Escuer et al., 1997). Synthesizing high-dimensional compounds with azide and negatively charged ligands represents then a challenge for researchers working in this field. (Liu et al., 2005)
In the title compound, the cadmium atom is six coordinated by two azide anions and three pyrazine-2-carboxylate (Fig. 1). Each pyrazine-2-carboxylate bridges three cadmium atoms whereas the azide is bridging two cadmium atoms resulting in the formation of a two dimensional metal organic polymer developping parallel to the (1 0 0) plane.