Acta Cryst. (2009). E65, m1160 [ doi:10.1107/S1600536809034369 ]
In the centrosymmetric title complex, [Cu(C6H5N6)2], the CuII ion is coordinated by four N atoms from two symmetry-related bidentate 5-(2-amino-3-pyridyl)tetrazolate ligands in a slightly distorted square-planar environment. There are weak intramolecular N-H
N hydrogen bonds between the two ligands. In the crystal structure, there are significant ![[pi]](/logos/entities/pi_rmgif.gif)
- stacking interactions between symmetry-related tetrazole and pyridine rings, with a centroid-centroid distance of 3.6025 (18)°.
The title compound was prepared by hydrothermal treatment of 2-aminonicotinonitrile (2.3 mmol) and Cu(NO3)2 (1.0 mmol) with excess amount of NaN3 in a sealed Pyrex tuble at 403K for 2–4 days. The resulting green rectangular crystals gave a yield of 75% based on Cu(NO3)2.
H atoms were placed in caculated positions with C-H = 0.93 and N-H = 0.90Å and refined using a riding-model approximation with Uiso(H) = 1.2Ueq(C,N).
Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
![[Figure 1]](./lh2827fig1thm.gif)
| Fig. 1. The molecular structure of the title compound with the atomic numbering scheme. Displacement ellipsoids were drawn at the 30% probability level. Symmetry code: (a) -x+1, -y+1, -z+1. Hydrogen bonds are shown as dashed lines. |
| [Cu(C6H5N6)2] | F(000) = 390 |
| Mr = 385.86 | Dx = 1.829 Mg m−3 |
| Monoclinic, P21/c | Melting point: 723 K |
| Hall symbol: -P 2ybc | Mo Kα radiation, λ = 0.71073 Å |
| a = 6.6492 (6) Å | Cell parameters from 2942 reflections |
| b = 7.9093 (7) Å | θ = 3.0–27.5° |
| c = 13.5581 (12) Å | µ = 1.59 mm−1 |
| β = 100.692 (2)° | T = 294 K |
| V = 700.65 (11) Å3 | Rectangle, green |
| Z = 2 | 0.15 × 0.13 × 0.09 mm |
| Rigaku Mercury2 diffractometer | 1363 independent reflections |
| Radiation source: fine-focus sealed tube | 1228 reflections with I > 2σ(I) |
| graphite | Rint = 0.020 |
| Detector resolution: 13.6612 pixels mm-1 | θmax = 26.0°, θmin = 3.0° |
| ω scans | h = −8→7 |
| Absorption correction: multi-scan (CrystalClear; Rigaku, 2005) | k = −8→9 |
| Tmin = 0.797, Tmax = 0.870 | l = −15→16 |
| 3743 measured reflections |
| 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)] = 0.040 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.109 | H-atom parameters constrained |
| S = 1.07 | w = 1/[σ2(Fo2) + (0.0555P)2 + 1.0273P] where P = (Fo2 + 2Fc2)/3 |
| 1363 reflections | (Δ/σ)max < 0.001 |
| 115 parameters | Δρmax = 0.69 e Å−3 |
| 0 restraints | Δρmin = −0.73 e Å−3 |
| [Cu(C6H5N6)2] | V = 700.65 (11) Å3 |
| Mr = 385.86 | Z = 2 |
| Monoclinic, P21/c | Mo Kα radiation |
| a = 6.6492 (6) Å | µ = 1.59 mm−1 |
| b = 7.9093 (7) Å | T = 294 K |
| c = 13.5581 (12) Å | 0.15 × 0.13 × 0.09 mm |
| β = 100.692 (2)° |
| Rigaku Mercury2 diffractometer | 1363 independent reflections |
| Absorption correction: multi-scan (CrystalClear; Rigaku, 2005) | 1228 reflections with I > 2σ(I) |
| Tmin = 0.797, Tmax = 0.870 | Rint = 0.020 |
| 3743 measured reflections | θmax = 26.0° |
| R[F2 > 2σ(F2)] = 0.040 | H-atom parameters constrained |
| wR(F2) = 0.109 | Δρmax = 0.69 e Å−3 |
| S = 1.07 | Δρmin = −0.73 e Å−3 |
| 1363 reflections | Absolute structure: ? |
| 115 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 | ||
| Cu1 | 0.5000 | 0.5000 | 0.5000 | 0.0265 (2) | |
| N6 | 1.0060 (4) | 0.1967 (3) | 0.61317 (18) | 0.0302 (6) | |
| C6 | 0.7920 (5) | 0.3986 (4) | 0.3685 (2) | 0.0260 (6) | |
| C5 | 0.9283 (4) | 0.3088 (4) | 0.4476 (2) | 0.0263 (6) | |
| N4 | 0.6177 (4) | 0.4748 (3) | 0.37835 (19) | 0.0294 (6) | |
| C4 | 0.8741 (5) | 0.2899 (4) | 0.5446 (2) | 0.0258 (6) | |
| N3 | 0.8245 (4) | 0.4167 (4) | 0.27476 (19) | 0.0345 (6) | |
| C3 | 1.1079 (5) | 0.2369 (4) | 0.4307 (2) | 0.0322 (7) | |
| H3A | 1.1439 | 0.2497 | 0.3680 | 0.039* | |
| N2 | 0.5399 (4) | 0.5422 (4) | 0.2875 (2) | 0.0365 (6) | |
| C2 | 1.2364 (5) | 0.1461 (4) | 0.5041 (3) | 0.0364 (7) | |
| H2A | 1.3576 | 0.0997 | 0.4914 | 0.044* | |
| C1 | 1.1816 (5) | 0.1263 (4) | 0.5947 (2) | 0.0349 (7) | |
| H1A | 1.2646 | 0.0642 | 0.6446 | 0.042* | |
| N1 | 0.6643 (5) | 0.5072 (4) | 0.2266 (2) | 0.0385 (7) | |
| N5 | 0.7116 (4) | 0.3534 (3) | 0.56979 (17) | 0.0291 (6) | |
| H5A | 0.7585 | 0.4076 | 0.6279 | 0.035* | |
| H5B | 0.6431 | 0.2629 | 0.5866 | 0.035* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Cu1 | 0.0241 (3) | 0.0352 (3) | 0.0227 (3) | 0.00433 (19) | 0.0104 (2) | 0.00138 (19) |
| N6 | 0.0281 (14) | 0.0330 (14) | 0.0300 (13) | 0.0006 (10) | 0.0068 (11) | 0.0029 (10) |
| C6 | 0.0267 (15) | 0.0296 (14) | 0.0243 (13) | −0.0035 (11) | 0.0112 (11) | −0.0035 (11) |
| C5 | 0.0250 (15) | 0.0270 (14) | 0.0292 (15) | −0.0012 (11) | 0.0108 (12) | −0.0019 (11) |
| N4 | 0.0280 (14) | 0.0395 (14) | 0.0223 (12) | 0.0041 (11) | 0.0087 (10) | 0.0012 (10) |
| C4 | 0.0239 (15) | 0.0258 (14) | 0.0286 (14) | −0.0029 (11) | 0.0076 (12) | 0.0000 (11) |
| N3 | 0.0342 (15) | 0.0477 (16) | 0.0248 (12) | 0.0030 (12) | 0.0137 (11) | −0.0019 (11) |
| C3 | 0.0325 (17) | 0.0347 (16) | 0.0328 (16) | 0.0011 (13) | 0.0151 (13) | −0.0031 (13) |
| N2 | 0.0353 (16) | 0.0513 (16) | 0.0245 (13) | 0.0073 (13) | 0.0100 (11) | 0.0046 (12) |
| C2 | 0.0280 (16) | 0.0374 (17) | 0.0464 (18) | 0.0065 (13) | 0.0141 (14) | −0.0028 (14) |
| C1 | 0.0297 (17) | 0.0334 (16) | 0.0393 (17) | 0.0024 (12) | 0.0002 (13) | 0.0015 (13) |
| N1 | 0.0365 (17) | 0.0561 (19) | 0.0242 (13) | 0.0054 (12) | 0.0092 (12) | 0.0040 (11) |
| N5 | 0.0277 (14) | 0.0401 (15) | 0.0229 (11) | 0.0069 (11) | 0.0135 (10) | 0.0056 (10) |
| Cu1—N5i | 1.930 (2) | N4—N2 | 1.354 (4) |
| Cu1—N5 | 1.930 (2) | C4—N5 | 1.293 (4) |
| Cu1—N4 | 1.963 (2) | N3—N1 | 1.348 (4) |
| Cu1—N4i | 1.963 (2) | C3—C2 | 1.386 (5) |
| N6—C1 | 1.358 (4) | C3—H3A | 0.9300 |
| N6—C4 | 1.369 (4) | N2—N1 | 1.302 (4) |
| C6—N4 | 1.335 (4) | C2—C1 | 1.354 (5) |
| C6—N3 | 1.336 (4) | C2—H2A | 0.9300 |
| C6—C5 | 1.455 (4) | C1—H1A | 0.9300 |
| C5—C3 | 1.380 (4) | N5—H5A | 0.9000 |
| C5—C4 | 1.435 (4) | N5—H5B | 0.9000 |
| N5i—Cu1—N5 | 180 | C6—N3—N1 | 105.3 (2) |
| N5i—Cu1—N4 | 90.97 (10) | C5—C3—C2 | 122.1 (3) |
| N5—Cu1—N4 | 89.03 (10) | C5—C3—H3A | 118.9 |
| N5i—Cu1—N4i | 89.03 (10) | C2—C3—H3A | 118.9 |
| N5—Cu1—N4i | 90.97 (10) | N1—N2—N4 | 108.2 (3) |
| N4—Cu1—N4i | 180 | C1—C2—C3 | 118.5 (3) |
| C1—N6—C4 | 124.1 (3) | C1—C2—H2A | 120.7 |
| N4—C6—N3 | 110.1 (3) | C3—C2—H2A | 120.7 |
| N4—C6—C5 | 125.5 (3) | C2—C1—N6 | 120.3 (3) |
| N3—C6—C5 | 124.4 (3) | C2—C1—H1A | 119.8 |
| C3—C5—C4 | 118.8 (3) | N6—C1—H1A | 119.8 |
| C3—C5—C6 | 121.3 (3) | N2—N1—N3 | 110.1 (3) |
| C4—C5—C6 | 119.9 (3) | C4—N5—Cu1 | 132.2 (2) |
| C6—N4—N2 | 106.2 (2) | C4—N5—H5A | 104.2 |
| C6—N4—Cu1 | 128.3 (2) | Cu1—N5—H5A | 104.2 |
| N2—N4—Cu1 | 125.5 (2) | C4—N5—H5B | 104.2 |
| N5—C4—N6 | 119.4 (3) | Cu1—N5—H5B | 104.2 |
| N5—C4—C5 | 124.5 (3) | H5A—N5—H5B | 105.5 |
| N6—C4—C5 | 116.1 (3) | ||
| N4—C6—C5—C3 | −178.6 (3) | C6—C5—C4—N6 | 176.9 (3) |
| N3—C6—C5—C3 | 1.2 (5) | N4—C6—N3—N1 | 0.1 (3) |
| N4—C6—C5—C4 | 3.1 (4) | C5—C6—N3—N1 | −179.8 (3) |
| N3—C6—C5—C4 | −177.1 (3) | C4—C5—C3—C2 | 0.5 (5) |
| N3—C6—N4—N2 | 0.1 (4) | C6—C5—C3—C2 | −177.8 (3) |
| C5—C6—N4—N2 | 179.9 (3) | C6—N4—N2—N1 | −0.2 (4) |
| N3—C6—N4—Cu1 | −176.5 (2) | Cu1—N4—N2—N1 | 176.5 (2) |
| C5—C6—N4—Cu1 | 3.4 (4) | C5—C3—C2—C1 | 0.8 (5) |
| N5—Cu1—N4—C6 | −7.2 (3) | C3—C2—C1—N6 | −1.1 (5) |
| N5—Cu1—N4—N2 | 176.9 (3) | C4—N6—C1—C2 | 0.1 (5) |
| C1—N6—C4—N5 | −179.3 (3) | N4—N2—N1—N3 | 0.2 (4) |
| C1—N6—C4—C5 | 1.2 (4) | C6—N3—N1—N2 | −0.2 (4) |
| C3—C5—C4—N5 | 179.0 (3) | N6—C4—N5—Cu1 | 175.8 (2) |
| C6—C5—C4—N5 | −2.6 (4) | C5—C4—N5—Cu1 | −4.7 (5) |
| C3—C5—C4—N6 | −1.4 (4) | N4—Cu1—N5—C4 | 8.1 (3) |
| Symmetry codes: (i) −x+1, −y+1, −z+1. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N5—H5A···N2i | 0.90 | 2.50 | 2.902 (4) | 108 |
| Symmetry codes: (i) −x+1, −y+1, −z+1. |
| N5i—Cu1—N5 | 180 | N5—Cu1—N4i | 90.97 (10) |
| N5—Cu1—N4 | 89.03 (10) | N4—Cu1—N4i | 180 |
| Symmetry codes: (i) −x+1, −y+1, −z+1. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N5—H5A···N2i | 0.90 | 2.50 | 2.902 (4) | 108 |
| Symmetry codes: (i) −x+1, −y+1, −z+1. |
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In situ [2+3] cycloaddition synthesis of tetrazole coordination polymers under hydrothermal conditions has proved to be a fast and convenient route to explore novel coordination polymers with rich structural diversities and potential physical properties, such as second harmonic generation (SGH), ferroelectric and dielectric responses (Xiong et al., 2002; Ye et al., 2006; Fu et al. (2008). The crystal structure of the compound formed by our hydrothermal synthesis is reported herein.
The molecular structure of the title compound is shown in Fig. 1. The CuII ion lies on an inversion center coordinated by four N atoms from two symmetry related bidentate 3-(2-Amino-pyridyl))tetrazolato ligands in a slightly distorted square-planar environment. In the crystal structure, there are significant π–π stacking interactions between symmetry related tetrazole and pyridine rings with a centroid to centroid distance of 3.6025 (18)°.