Acta Cryst. (2009). E65, m671 [ doi:10.1107/S1600536809018649 ]
![[mu]](/logos/entities/mu_rmgif.gif)
-aqua--4-(5-tetrazolio)pyridine]The title compound, [K(C6H4N5)(H2O)2]n, was synthesized by hydrothermal reaction of KOH with 4-(5-tetrazolio)pyridine. The K atom has a distorted octahedral coordination environment and is coordinated by two axial N atoms from the organic ligand and by four water molecules in the equatorial plane. The molecules as a whole are located on crystallographic mirror planes; the K atom is also located on an inversion center. Both the water molecules and the organic ligands act as bridges to link symmetrically the adjacent K atoms into polymeric chains parallel to the c axis. O-H
N hydrogen bonds involving the water O atoms and aromatic ![[pi]](/logos/entities/pi_rmgif.gif)
- interactions [centroid-centroid distance 3.80 (2) Å] between the pyridine and tetrazole rings build up an infinite three-dimensional network.
A mixture of 4-(2H-tetrazol-5-yl)pyridine (0.4 mmol) and KOH (0.4 mmol), ethanol (1 ml) and a few drops of water sealed in a glass tube was maintained at 373 K. Colorless needle crystals suitable for X-ray analysis were obtained after 3 days.
All H atoms attached to C atoms were fixed geometrically and treated as riding with C–H = 0.93 Å (aromatic) with Uiso(H) = 1.2Ueq(C). The H atoms of water molecules were located in difference Fourier maps and the O–H distances were restrained in the subsequent refinements to 0.85 Å with Uiso(H) =1.5Ueq(O). In the last stage of the refinement they were treated as riding on the O atom.
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: SHELXTL (Version 5.1; Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Version 5.1; Sheldrick, 2008).
![[Figure 1]](./zl2195fig1thm.gif)
| Fig. 1. A view of the title compound with the atomic numbering scheme. Displacement ellipsoids were drawn at the 30% probability level. |
![[Figure 2]](./zl2195fig2thm.gif)
| Fig. 2. The crystal packing of the title compound viewed along the c axis showing the three dimensionnal network (dashed lines). Hydrogen atoms not involved in hydrogen bonding have been omitted for clarity. |
| [K(C6H4N5)(H2O)2] | F000 = 456 |
| Mr = 221.27 | Dx = 1.483 Mg m−3 |
| Monoclinic, C2/c | Mo Kα radiation λ = 0.71073 Å |
| Hall symbol: -C 2yc | Cell parameters from 1134 reflections |
| a = 12.361 (3) Å | θ = 3.3–27.5º |
| b = 12.281 (3) Å | µ = 0.52 mm−1 |
| c = 7.3431 (15) Å | T = 298 K |
| β = 117.25 (3)º | Needle, colorless |
| V = 991.1 (3) Å3 | 0.25 × 0.15 × 0.10 mm |
| Z = 4 |
| Rigaku Mercury2 (2× 2 bin mode) diffractometer | 1134 independent reflections |
| Radiation source: fine-focus sealed tube | 928 reflections with I > 2σ(I) |
| Monochromator: graphite | Rint = 0.027 |
| Detector resolution: 13.6612 pixels mm-1 | θmax = 27.5º |
| T = 298 K | θmin = 3.3º |
| ω scans | h = −16→16 |
| Absorption correction: multi-scan (CrystalClear; Rigaku, 2005) | k = −15→15 |
| Tmin = 0.913, Tmax = 1.000 | l = −9→9 |
| 5056 measured reflections |
| Refinement on F2 | Secondary atom site location: difference Fourier map |
| Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
| R[F2 > 2σ(F2)] = 0.037 | H-atom parameters constrained |
| wR(F2) = 0.096 | w = 1/[σ2(Fo2) + (0.039P)2 + 0.7641P] where P = (Fo2 + 2Fc2)/3 |
| S = 1.07 | (Δ/σ)max < 0.001 |
| 1134 reflections | Δρmax = 0.32 e Å−3 |
| 67 parameters | Δρmin = −0.19 e Å−3 |
| 2 restraints | Extinction correction: none |
| Primary atom site location: structure-invariant direct methods |
| [K(C6H4N5)(H2O)2] | V = 991.1 (3) Å3 |
| Mr = 221.27 | Z = 4 |
| Monoclinic, C2/c | Mo Kα |
| a = 12.361 (3) Å | µ = 0.52 mm−1 |
| b = 12.281 (3) Å | T = 298 K |
| c = 7.3431 (15) Å | 0.25 × 0.15 × 0.10 mm |
| β = 117.25 (3)º |
| Rigaku Mercury2 (2× 2 bin mode) diffractometer | 1134 independent reflections |
| Absorption correction: multi-scan (CrystalClear; Rigaku, 2005) | 928 reflections with I > 2σ(I) |
| Tmin = 0.913, Tmax = 1.000 | Rint = 0.027 |
| 5056 measured reflections |
| R[F2 > 2σ(F2)] = 0.037 | 2 restraints |
| wR(F2) = 0.096 | H-atom parameters constrained |
| S = 1.07 | Δρmax = 0.32 e Å−3 |
| 1134 reflections | Δρmin = −0.19 e Å−3 |
| 67 parameters |
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 | ||
| K1 | 0.5000 | 0.0000 | 0.5000 | 0.0467 (2) | |
| C4 | 0.5000 | 0.5325 (2) | 0.7500 | 0.0365 (6) | |
| C3 | 0.5000 | 0.4124 (2) | 0.7500 | 0.0358 (5) | |
| N2 | 0.60000 (14) | 0.59305 (13) | 0.8162 (3) | 0.0468 (4) | |
| C2 | 0.60283 (18) | 0.35391 (16) | 0.7821 (3) | 0.0459 (5) | |
| H2 | 0.6742 | 0.3897 | 0.8050 | 0.055* | |
| N3 | 0.55965 (15) | 0.69599 (13) | 0.7896 (3) | 0.0530 (5) | |
| N1 | 0.5000 | 0.18446 (19) | 0.7500 | 0.0522 (6) | |
| C1 | 0.5980 (2) | 0.24208 (17) | 0.7797 (4) | 0.0534 (5) | |
| H1 | 0.6678 | 0.2041 | 0.8000 | 0.064* | |
| O1W | 0.34559 (12) | 0.08972 (11) | 0.1308 (2) | 0.0516 (4) | |
| H1WA | 0.2731 | 0.0885 | 0.0381 | 0.077* | |
| H1WB | 0.3654 | 0.1588 | 0.1421 | 0.077* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| K1 | 0.0545 (4) | 0.0460 (4) | 0.0403 (3) | −0.0005 (3) | 0.0221 (3) | −0.0025 (3) |
| C4 | 0.0345 (13) | 0.0344 (12) | 0.0323 (13) | 0.000 | 0.0080 (11) | 0.000 |
| C3 | 0.0381 (13) | 0.0334 (13) | 0.0296 (12) | 0.000 | 0.0102 (10) | 0.000 |
| N2 | 0.0383 (9) | 0.0337 (8) | 0.0522 (10) | −0.0025 (7) | 0.0067 (7) | −0.0016 (7) |
| C2 | 0.0392 (10) | 0.0406 (10) | 0.0536 (12) | −0.0008 (8) | 0.0176 (9) | −0.0029 (9) |
| N3 | 0.0503 (9) | 0.0340 (8) | 0.0541 (11) | −0.0042 (7) | 0.0062 (8) | −0.0020 (7) |
| N1 | 0.0602 (16) | 0.0343 (12) | 0.0524 (15) | 0.000 | 0.0174 (13) | 0.000 |
| C1 | 0.0514 (12) | 0.0416 (11) | 0.0596 (13) | 0.0090 (9) | 0.0189 (10) | −0.0026 (9) |
| O1W | 0.0341 (7) | 0.0376 (7) | 0.0667 (10) | 0.0014 (6) | 0.0088 (7) | 0.0026 (6) |
| K1—O1Wi | 2.7309 (16) | C3—C2iv | 1.383 (2) |
| K1—O1Wii | 2.7309 (16) | C3—C2 | 1.383 (2) |
| K1—O1W | 2.7330 (17) | N2—N3 | 1.340 (2) |
| K1—O1Wiii | 2.7330 (17) | C2—C1 | 1.375 (3) |
| K1—N1iii | 2.9159 (18) | C2—H2 | 0.9300 |
| K1—N1 | 2.9159 (18) | N3—N3iv | 1.314 (3) |
| K1—C1iii | 3.499 (2) | N1—C1 | 1.332 (3) |
| K1—C1 | 3.499 (2) | N1—C1iv | 1.332 (3) |
| K1—K1ii | 3.6716 (7) | N1—K1iv | 2.9159 (18) |
| K1—K1iv | 3.6716 (8) | C1—H1 | 0.9300 |
| K1—H1WB | 3.0780 | O1W—K1ii | 2.7309 (16) |
| C4—N2 | 1.329 (2) | O1W—H1WA | 0.8412 |
| C4—N2iv | 1.329 (2) | O1W—H1WB | 0.8765 |
| C4—C3 | 1.475 (3) | ||
| O1Wi—K1—O1Wii | 180.00 (3) | C1iii—K1—K1iv | 115.36 (4) |
| O1Wi—K1—O1W | 103.20 (5) | C1—K1—K1iv | 64.64 (4) |
| O1Wii—K1—O1W | 76.80 (5) | K1ii—K1—K1iv | 180.0 |
| O1Wi—K1—O1Wiii | 76.80 (5) | O1Wi—K1—H1WB | 111.4 |
| O1Wii—K1—O1Wiii | 103.20 (5) | O1Wii—K1—H1WB | 68.6 |
| O1W—K1—O1Wiii | 180.0 | O1W—K1—H1WB | 16.0 |
| O1Wi—K1—N1iii | 96.28 (4) | O1Wiii—K1—H1WB | 164.0 |
| O1Wii—K1—N1iii | 83.72 (4) | N1iii—K1—H1WB | 96.4 |
| O1W—K1—N1iii | 83.68 (4) | N1—K1—H1WB | 83.6 |
| O1Wiii—K1—N1iii | 96.32 (4) | C1iii—K1—H1WB | 97.5 |
| O1Wi—K1—N1 | 83.72 (4) | C1—K1—H1WB | 82.5 |
| O1Wii—K1—N1 | 96.28 (4) | K1ii—K1—H1WB | 52.7 |
| O1W—K1—N1 | 96.32 (4) | K1iv—K1—H1WB | 127.3 |
| O1Wiii—K1—N1 | 83.68 (4) | N2—C4—N2iv | 112.0 (2) |
| N1iii—K1—N1 | 180.0 | N2—C4—C3 | 124.01 (11) |
| O1Wi—K1—C1iii | 75.74 (5) | N2iv—C4—C3 | 124.01 (11) |
| O1Wii—K1—C1iii | 104.26 (5) | C2iv—C3—C2 | 117.4 (2) |
| O1W—K1—C1iii | 82.15 (5) | C2iv—C3—C4 | 121.30 (12) |
| O1Wiii—K1—C1iii | 97.85 (5) | C2—C3—C4 | 121.30 (12) |
| N1iii—K1—C1iii | 21.60 (4) | C4—N2—N3 | 104.64 (16) |
| N1—K1—C1iii | 158.40 (4) | C1—C2—C3 | 119.1 (2) |
| O1Wi—K1—C1 | 104.26 (5) | C1—C2—H2 | 120.5 |
| O1Wii—K1—C1 | 75.74 (5) | C3—C2—H2 | 120.5 |
| O1W—K1—C1 | 97.85 (5) | N3iv—N3—N2 | 109.38 (10) |
| O1Wiii—K1—C1 | 82.15 (5) | C1—N1—C1iv | 115.8 (2) |
| N1iii—K1—C1 | 158.40 (4) | C1—N1—K1 | 104.69 (11) |
| N1—K1—C1 | 21.60 (4) | C1iv—N1—K1 | 124.89 (11) |
| C1iii—K1—C1 | 180.00 (9) | C1—N1—K1iv | 124.89 (11) |
| O1Wi—K1—K1ii | 132.19 (4) | C1iv—N1—K1iv | 104.69 (11) |
| O1Wii—K1—K1ii | 47.81 (4) | K1—N1—K1iv | 78.04 (6) |
| O1W—K1—K1ii | 47.76 (3) | N1—C1—C2 | 124.3 (2) |
| O1Wiii—K1—K1ii | 132.24 (3) | N1—C1—K1 | 53.71 (10) |
| N1iii—K1—K1ii | 50.98 (3) | C2—C1—K1 | 149.08 (16) |
| N1—K1—K1ii | 129.02 (3) | N1—C1—H1 | 117.8 |
| C1iii—K1—K1ii | 64.64 (4) | C2—C1—H1 | 117.8 |
| C1—K1—K1ii | 115.36 (4) | K1—C1—H1 | 73.4 |
| O1Wi—K1—K1iv | 47.81 (4) | K1ii—O1W—K1 | 84.44 (4) |
| O1Wii—K1—K1iv | 132.19 (4) | K1ii—O1W—H1WA | 111.4 |
| O1W—K1—K1iv | 132.24 (3) | K1—O1W—H1WA | 142.8 |
| O1Wiii—K1—K1iv | 47.76 (3) | K1ii—O1W—H1WB | 102.4 |
| N1iii—K1—K1iv | 129.02 (3) | K1—O1W—H1WB | 105.0 |
| N1—K1—K1iv | 50.98 (3) | H1WA—O1W—H1WB | 104.0 |
| Symmetry codes: (i) x, −y, z+1/2; (ii) −x+1, y, −z+1/2; (iii) −x+1, −y, −z+1; (iv) −x+1, y, −z+3/2. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O1W—H1WA···N2v | 0.84 | 2.01 | 2.852 (2) | 177 |
| O1W—H1WB···N3vi | 0.88 | 1.97 | 2.831 (2) | 169 |
| Symmetry codes: (v) x−1/2, y−1/2, z−1; (vi) −x+1, −y+1, −z+1. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O1W—H1WA···N2i | 0.84 | 2.01 | 2.852 (2) | 177 |
| O1W—H1WB···N3ii | 0.88 | 1.97 | 2.831 (2) | 169 |
| Symmetry codes: (i) x−1/2, y−1/2, z−1; (ii) −x+1, −y+1, −z+1. |
This work was supported by a Start-up Grant from Southeast University to Professor Ren-Gen Xiong.
Dai, W. & Fu, D.-W. (2008). Acta Cryst. E64, o1444.
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Wang, X.-S., Tang, Y.-Z., Huang, X.-F., Qu, Z.-R., Che, C.-M., Chan, C. W. H. & Xiong, R.-G. (2005). Inorg. Chem. 44, 5278–5285.
Xiong, R.-G., Xue, X., Zhao, H., You, X.-Z., Abrahams, B. F. & Xue, Z.-L. (2002). Angew. Chem. Int. Ed. 41, 3800–3803.
In the past few years, more and more people have focused on the chemistry of tetrazole derivatives because of their multiple coordination modes as ligands to metal ions and for the construction of novel metal-organic frameworks (Wang, et al. 2005; Xiong, et al. 2002). We report here the crystal structure of the title compound, tetra-aqua-bis[4-(2H-tetrazol-5-yl)pyridine]potassium(I).
The K atom has a distorted octahedral geometry and is coordinated by two axial pyridyl N atoms from the organic ligand and four water molecules ligands in the equatorial plane. The molecules as a whole are located on crystallographic mirror planes, the potassium ion is also located on an inversion center. Both the water molecules and the organic ligands act as bridges linking adjacent K ions into polymeric chains parallel to the c axis by covalent bonds (K—N, and K—O). The pyridine and tetrazole rings are nearly coplanar and are twisted from each other by a dihedral angle of only 12.99 (0.13) ° (Fig.1). The bond distances and bond angles of the tetrazole rings are in the usual ranges (Wang, et al. 2005; Dai & Fu 2008).
The crystal packing (Fig. 2) is stabilized by aromatic π–π interactions between the pyridine and tetrazole rings of the neighbouring ligand systems. The centroid···centroid distance is 3.80 (2)Å (symmetry code: x, y, z+1 and x, y, z). The molecular packing is further stabilized by intermolecular O—H···N hydrogen bonds involving the aqueous O atoms. The π–π and hydrogen bonding interactions build up an infinite three-dimensional network. (Fig. 2 and Table 1).