Acta Cryst. (2010). E66, m217 [ doi:10.1107/S1600536810001431 ]
![[mu]](/logos/entities/mu_rmgif.gif)
2-3,6-di-4-pyridyl-1,2,4,5-tetrazine)(2-thiocyanato)copper(I)]The title compound, [Cu(NCS)(C12H8N6)]n, is a self-assembled two-dimensional metal-organic network. The Cu atom is linked by two N atoms from two 3,6-di-4-pyridyl-1,2,4,5-tetrazine ligands and by the N and S atoms from two thiocyanate ligands in a distorted tetrahedral environment. The Cu atom and the thiocyanate ligand occupy a crystallographic mirror plane m, and a crystallographic inversion centre is in the middle of the tetrazine ring, generating the zigzag fashion of the two-dimensional network. The infinite -Cu-SCN-Cu-SCN- chain is due to translational symmetry along the a axis. These chains are further connected through the 3,6-di-4-pyridyl-1,2,4,5-tetrazine ligands that bridge the CuI centers, generating a two-dimensional network. There are ![[pi]](/logos/entities/pi_rmgif.gif)
- stacking interactions between the pyridine and tetrazine rings (perpendicular distances of 3.357 and 3.418 Å), with a centroid-centroid distance of 3.6785 (16) Å.
CuSCN (12.2 mg) and NH4SCN(1.4 mg) were added into 2.5 ml DMF and the solution were stirred for 10 min at room temperature until became clarification. Then, the resulting solution was subsequently filterated to a tube, then 2.5 ml solution of i.-pron and 3,6-di-4-pyridyl-1,2,4,5-tetrazine added to afford a black filtrate. Many prismatic black crystals were obtained a few weeks later.
H atoms were positioned geometrically and refined as a riding model, with Uiso(H) = 1.2Ueq (pyridyl C atoms). The C—H bond lengths are 0.93 Å.
Data collection: CrystalClear (Rigaku, 2008); cell refinement: CrystalClear (Rigaku, 2008); data reduction: CrystalClear (Rigaku, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).
![[Figure 1]](./si2230fig1thm.gif)
| Fig. 1. A section of the two-dimensional structure of the title complex, with atom labels and 30% probability displacement ellipsoids. H atoms have been omitted. [symmetry codes: i = -1 + x, y, z; ii = 1 + x, y, z; iii = x, 1/2 - y, z; iv = -1 - x, -y, 1 - z.] |
![[Figure 2]](./si2230fig2thm.gif)
| Fig. 2. The unit cell packing diagram. |
| [Cu(NCS)(C12H8N6)] | F(000) = 360 |
| Mr = 357.88 | Dx = 1.767 Mg m−3 |
| Monoclinic, P21/m | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -P 2yb | Cell parameters from 2914 reflections |
| a = 5.8640 (12) Å | θ = 3.3–28.9° |
| b = 18.510 (4) Å | µ = 1.79 mm−1 |
| c = 6.3993 (13) Å | T = 250 K |
| β = 104.42 (3)° | Prism, black |
| V = 672.7 (2) Å3 | 0.20 × 0.20 × 0.20 mm |
| Z = 2 |
| Rigaku Mercury diffractometer | 1373 independent reflections |
| Radiation source: fine-focus sealed tube | 1304 reflections with I > 2σ(I) |
| graphite | Rint = 0.018 |
| Detector resolution: 28.5714 pixels mm-1 | θmax = 26.4°, θmin = 3.3° |
| dtprofit.ref scans | h = −7→5 |
| Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | k = −22→20 |
| Tmin = 0.445, Tmax = 0.738 | l = −8→7 |
| 3288 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)] = 0.033 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.069 | H-atom parameters constrained |
| S = 1.11 | w = 1/[σ2(Fo2) + (0.0163P)2 + 0.7211P] where P = (Fo2 + 2Fc2)/3 |
| 1373 reflections | (Δ/σ)max < 0.001 |
| 106 parameters | Δρmax = 0.48 e Å−3 |
| 0 restraints | Δρmin = −0.36 e Å−3 |
| [Cu(NCS)(C12H8N6)] | V = 672.7 (2) Å3 |
| Mr = 357.88 | Z = 2 |
| Monoclinic, P21/m | Mo Kα radiation |
| a = 5.8640 (12) Å | µ = 1.79 mm−1 |
| b = 18.510 (4) Å | T = 250 K |
| c = 6.3993 (13) Å | 0.20 × 0.20 × 0.20 mm |
| β = 104.42 (3)° |
| Rigaku Mercury diffractometer | 1373 independent reflections |
| Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | 1304 reflections with I > 2σ(I) |
| Tmin = 0.445, Tmax = 0.738 | Rint = 0.018 |
| 3288 measured reflections | θmax = 26.4° |
| R[F2 > 2σ(F2)] = 0.033 | H-atom parameters constrained |
| wR(F2) = 0.069 | Δρmax = 0.48 e Å−3 |
| S = 1.11 | Δρmin = −0.36 e Å−3 |
| 1373 reflections | Absolute structure: ? |
| 106 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 | −0.50890 (7) | 0.2500 | −0.44195 (7) | 0.03870 (15) | |
| S1 | −0.83431 (16) | 0.2500 | −0.71812 (15) | 0.0502 (3) | |
| N1 | −0.5137 (3) | 0.16473 (11) | −0.2265 (3) | 0.0379 (5) | |
| N2 | −1.2068 (5) | 0.2500 | −0.5169 (5) | 0.0454 (7) | |
| N3 | −0.7033 (4) | 0.00418 (13) | 0.3425 (3) | 0.0465 (5) | |
| N4 | −0.3006 (4) | 0.03426 (13) | 0.4828 (3) | 0.0467 (5) | |
| C1 | −0.7064 (4) | 0.12996 (14) | −0.2042 (4) | 0.0407 (6) | |
| H1A | −0.8441 | 0.1346 | −0.3131 | 0.049* | |
| C2 | −0.5081 (4) | 0.07992 (13) | 0.1348 (4) | 0.0351 (5) | |
| C3 | −0.7118 (4) | 0.08763 (14) | −0.0286 (4) | 0.0407 (6) | |
| H3A | −0.8500 | 0.0646 | −0.0198 | 0.049* | |
| C4 | −0.5051 (4) | 0.03705 (13) | 0.3302 (4) | 0.0373 (5) | |
| C5 | −0.3166 (5) | 0.15430 (15) | −0.0716 (4) | 0.0436 (6) | |
| H5A | −0.1789 | 0.1761 | −0.0871 | 0.052* | |
| C6 | −0.3058 (4) | 0.11312 (14) | 0.1092 (4) | 0.0417 (6) | |
| H6A | −0.1643 | 0.1077 | 0.2129 | 0.050* | |
| C7 | −1.0503 (6) | 0.2500 | −0.5953 (5) | 0.0374 (8) |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Cu1 | 0.0309 (2) | 0.0500 (3) | 0.0350 (2) | 0.000 | 0.00798 (17) | 0.000 |
| S1 | 0.0272 (4) | 0.0901 (8) | 0.0326 (5) | 0.000 | 0.0059 (3) | 0.000 |
| N1 | 0.0372 (11) | 0.0403 (11) | 0.0357 (11) | 0.0029 (9) | 0.0079 (9) | 0.0063 (9) |
| N2 | 0.0297 (15) | 0.057 (2) | 0.0506 (19) | 0.000 | 0.0111 (14) | 0.000 |
| N3 | 0.0462 (13) | 0.0554 (14) | 0.0363 (11) | −0.0009 (11) | 0.0070 (9) | 0.0117 (10) |
| N4 | 0.0458 (13) | 0.0558 (14) | 0.0369 (11) | −0.0005 (11) | 0.0075 (10) | 0.0097 (10) |
| C1 | 0.0349 (13) | 0.0462 (14) | 0.0386 (13) | 0.0031 (11) | 0.0047 (10) | 0.0071 (11) |
| C2 | 0.0429 (13) | 0.0324 (12) | 0.0305 (11) | 0.0032 (10) | 0.0101 (10) | −0.0016 (10) |
| C3 | 0.0353 (12) | 0.0444 (14) | 0.0432 (14) | 0.0002 (11) | 0.0112 (11) | 0.0081 (11) |
| C4 | 0.0430 (14) | 0.0361 (13) | 0.0334 (12) | 0.0040 (11) | 0.0105 (10) | −0.0004 (10) |
| C5 | 0.0376 (13) | 0.0484 (15) | 0.0426 (14) | −0.0044 (12) | 0.0060 (11) | 0.0072 (12) |
| C6 | 0.0391 (13) | 0.0483 (15) | 0.0340 (13) | −0.0009 (11) | 0.0024 (10) | 0.0035 (11) |
| C7 | 0.0297 (17) | 0.046 (2) | 0.0330 (17) | 0.000 | 0.0008 (14) | 0.000 |
| Cu1—N2i | 1.948 (3) | N4—N3iv | 1.321 (3) |
| Cu1—N1ii | 2.100 (2) | N4—C4 | 1.346 (3) |
| Cu1—N1 | 2.100 (2) | C1—C3 | 1.377 (3) |
| Cu1—S1 | 2.2550 (13) | C1—H1A | 0.9300 |
| S1—C7 | 1.648 (4) | C2—C6 | 1.381 (3) |
| N1—C5 | 1.336 (3) | C2—C3 | 1.385 (3) |
| N1—C1 | 1.339 (3) | C2—C4 | 1.477 (3) |
| N2—C7 | 1.150 (4) | C3—H3A | 0.9300 |
| N2—Cu1iii | 1.948 (3) | C5—C6 | 1.374 (3) |
| N3—N4iv | 1.321 (3) | C5—H5A | 0.9300 |
| N3—C4 | 1.332 (3) | C6—H6A | 0.9300 |
| N2i—Cu1—N1ii | 108.87 (8) | C6—C2—C3 | 118.0 (2) |
| N2i—Cu1—N1 | 108.87 (8) | C6—C2—C4 | 120.7 (2) |
| N1ii—Cu1—N1 | 97.43 (11) | C3—C2—C4 | 121.4 (2) |
| N2i—Cu1—S1 | 116.81 (10) | C1—C3—C2 | 119.0 (2) |
| N1ii—Cu1—S1 | 111.55 (6) | C1—C3—H3A | 120.5 |
| N1—Cu1—S1 | 111.55 (6) | C2—C3—H3A | 120.5 |
| C7—S1—Cu1 | 103.11 (12) | N3—C4—N4 | 125.0 (2) |
| C5—N1—C1 | 116.6 (2) | N3—C4—C2 | 118.0 (2) |
| C5—N1—Cu1 | 116.43 (17) | N4—C4—C2 | 117.1 (2) |
| C1—N1—Cu1 | 125.52 (16) | N1—C5—C6 | 123.7 (2) |
| C7—N2—Cu1iii | 168.8 (3) | N1—C5—H5A | 118.1 |
| N4iv—N3—C4 | 117.7 (2) | C6—C5—H5A | 118.1 |
| N3iv—N4—C4 | 117.3 (2) | C5—C6—C2 | 119.1 (2) |
| N1—C1—C3 | 123.5 (2) | C5—C6—H6A | 120.5 |
| N1—C1—H1A | 118.2 | C2—C6—H6A | 120.5 |
| C3—C1—H1A | 118.2 | N2—C7—S1 | 177.5 (3) |
| Symmetry codes: (i) x+1, y, z; (ii) x, −y+1/2, z; (iii) x−1, y, z; (iv) −x−1, −y, −z+1. |
| Cu1—N2i | 1.948 (3) | Cu1—N1 | 2.100 (2) |
| Cu1—N1ii | 2.100 (2) | Cu1—S1 | 2.2550 (13) |
| Symmetry codes: (i) x+1, y, z; (ii) x, −y+1/2, z. |
This work was supported by the National Natural Science Foundation of China (No. 50472048).
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The coordination polymers that based on metal halides and N-donor ligands are one of the most important and promising fields in magnetism, nonlinear optics, electronics, catalysis and molecular topologies (Oxtoby et al., 2003; Hsu et al., 2006), the title compound is an example.
Many different coordination modes' polymers can be obtained by 3,6-di-4-pyridyl-1,2,4,5-tetrazine ligands because it can connect two different metal cations, and the Cu atom in CuSCN can be linked by linear spacer ligands into sheets (Dinolfo et al., 2004; Hsu et al., 2006). We obtained a two-dimensional metal-organic compound as the title complex, C13H8CuN7S (Fig. 1), whose structure contains single [CuSCN] ribbons as a characteristic motif. The asymmetric unit of the title compound consist of a half 3,6-di-4-pyridyl-1,2,4,5-tetrazine ligand, half a copper(I) and one SCN . group. Each Cu atom connected by three N atoms and one S atom, give rise to a distorted tetrahedron (Table 1). The layers can be described as formed by two types of perpendicular zigzag like chains crossing at the CuI centers. Chains of the first type run along the b-axis and have 3,6-di-4-pyridyl-1,2,4,5-tetrazine as a bridging ligand, while the second type extend along the a-axis containing bridging thiocyanate ligands. The structure is stabilized through π—π stacking interactions which can be imagined in Figure 2, with perpendicular distances between pyridine and tetrazine rings of 3.357 Å [symmetry code for Cg2tetrazine: x, y, -1 + z), and of 3.418 Å [symmetry code for Cg1pyridine: x, y, 1 + z); the Cg1···Cg2 distance is 3.6785 (16) Å. Cg1 and Cg2 are the centroids of rings (N1, C1, C3, C2, C6, C5) and (N3, C4, N4, N3iv, C4iv, N4iv), symmetry code iv = -1 - x, -y, 1 - z.