Acta Cryst. (2009). E65, o1318 [ doi:10.1107/S1600536809018078 ]
In the cation of the title compound, C6H6N5+·NO3-, the dihedral angle between the pyridinium and tetrazole rings is 8.2 (2)°. The constituent ions of the compound are linked via N-H
O hydrogen bonds, forming helical chains running along the b axis. C-HN and C-HO hydrogen bonds are also observed.
Picolinonitrile (30 mmol), NaN3 (45 mmol), NH4Cl (33 mmol) and DMF (50 ml) were added in a flask under nitrogen atmosphere. The mixture stirred at 110°C for 20 h. The resulting solution was then poured into ice-water (100 ml), and a white solid was obtained after adding HCl (6 M) at pH = 6. The precipitate was filtered and washed with distilled water. Colourless block-shaped crystals suitable for X-ray analysis were obtained from the crude product by slow evaporation of an ethanol-HNO3 (50:1 v/v) solution.
All H atoms attached to C and N atoms were fixed geometrically and treated as riding, with C–H = 0.93 Å, N–H = 0.86 Å and Uiso(H) =1.2Ueq(C or 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: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
![[Figure 1]](./ci2780fig1thm.gif)
| Fig. 1. A view of the title compound with the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. |
![[Figure 2]](./ci2780fig2thm.gif)
| Fig. 2. Partial packing view of the title compound showing the formation of chains along the b axis. H atoms not involved in hydrogen bonding (dashed lines) have been omitted for clarity. |
| C6H6N5+·NO3– | F000 = 864 |
| Mr = 210.17 | Dx = 1.608 Mg m−3 |
| Monoclinic, C2/c | Mo Kα radiation λ = 0.71073 Å |
| Hall symbol: -C 2yc | Cell parameters from 1999 reflections |
| a = 20.400 (4) Å | θ = 3.8–27.5º |
| b = 4.8981 (10) Å | µ = 0.13 mm−1 |
| c = 19.135 (4) Å | T = 298 K |
| β = 114.77 (3)º | Block, colourless |
| V = 1736.1 (7) Å3 | 0.20 × 0.15 × 0.15 mm |
| Z = 8 |
| Rigaku Mercury2 diffractometer | 1999 independent reflections |
| Radiation source: fine-focus sealed tube | 1033 reflections with I > 2σ(I) |
| Monochromator: graphite | Rint = 0.123 |
| Detector resolution: 13.6612 pixels mm-1 | θmax = 27.5º |
| T = 298 K | θmin = 3.8º |
| ω scans | h = −26→26 |
| Absorption correction: multi-scan (CrystalClear, Rigaku, 2005) | k = −6→6 |
| Tmin = 0.976, Tmax = 0.980 | l = −24→24 |
| 8427 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)] = 0.081 | H-atom parameters constrained |
| wR(F2) = 0.209 | w = 1/[σ2(Fo2) + (0.0838P)2] where P = (Fo2 + 2Fc2)/3 |
| S = 1.04 | (Δ/σ)max = 0.001 |
| 1999 reflections | Δρmax = 0.34 e Å−3 |
| 136 parameters | Δρmin = −0.36 e Å−3 |
| Primary atom site location: structure-invariant direct methods | Extinction correction: none |
| C6H6N5+·NO3– | V = 1736.1 (7) Å3 |
| Mr = 210.17 | Z = 8 |
| Monoclinic, C2/c | Mo Kα |
| a = 20.400 (4) Å | µ = 0.13 mm−1 |
| b = 4.8981 (10) Å | T = 298 K |
| c = 19.135 (4) Å | 0.20 × 0.15 × 0.15 mm |
| β = 114.77 (3)º |
| Rigaku Mercury2 diffractometer | 1999 independent reflections |
| Absorption correction: multi-scan (CrystalClear, Rigaku, 2005) | 1033 reflections with I > 2σ(I) |
| Tmin = 0.976, Tmax = 0.980 | Rint = 0.123 |
| 8427 measured reflections |
| R[F2 > 2σ(F2)] = 0.081 | 136 parameters |
| wR(F2) = 0.209 | H-atom parameters constrained |
| S = 1.04 | Δρmax = 0.34 e Å−3 |
| 1999 reflections | Δρmin = −0.36 e Å−3 |
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 | ||
| N1 | 0.11658 (15) | 0.9420 (6) | 0.51774 (16) | 0.0383 (7) | |
| H1 | 0.1239 | 1.0055 | 0.5623 | 0.046* | |
| C6 | 0.21176 (18) | 0.6182 (7) | 0.58420 (19) | 0.0362 (8) | |
| N2 | 0.24979 (17) | 0.3908 (6) | 0.58539 (17) | 0.0485 (8) | |
| C1 | 0.15732 (18) | 0.7297 (7) | 0.51387 (19) | 0.0364 (8) | |
| N5 | 0.23230 (16) | 0.7307 (6) | 0.65302 (17) | 0.0447 (8) | |
| C3 | 0.0917 (2) | 0.7442 (8) | 0.3768 (2) | 0.0506 (10) | |
| H3 | 0.0831 | 0.6771 | 0.3283 | 0.061* | |
| N4 | 0.28398 (16) | 0.5624 (6) | 0.69580 (17) | 0.0463 (8) | |
| H4A | 0.3082 | 0.5846 | 0.7445 | 0.056* | |
| N3 | 0.29538 (17) | 0.3572 (7) | 0.65769 (18) | 0.0518 (9) | |
| C4 | 0.0518 (2) | 0.9615 (9) | 0.3841 (2) | 0.0520 (11) | |
| H4 | 0.0161 | 1.0411 | 0.3408 | 0.062* | |
| C2 | 0.14442 (19) | 0.6270 (8) | 0.4418 (2) | 0.0436 (9) | |
| H2 | 0.1711 | 0.4798 | 0.4371 | 0.052* | |
| C5 | 0.0657 (2) | 1.0571 (8) | 0.4558 (2) | 0.0446 (9) | |
| H5 | 0.0395 | 1.2039 | 0.4615 | 0.053* | |
| N6 | 0.41263 (16) | 0.8821 (6) | 0.85439 (18) | 0.0434 (8) | |
| O3 | 0.37035 (14) | 0.6773 (5) | 0.84530 (13) | 0.0533 (8) | |
| O2 | 0.44457 (14) | 0.9758 (6) | 0.91958 (15) | 0.0570 (8) | |
| O1 | 0.41958 (16) | 0.9759 (6) | 0.79835 (16) | 0.0672 (9) |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| N1 | 0.0387 (17) | 0.0438 (18) | 0.0341 (16) | −0.0043 (14) | 0.0169 (14) | −0.0018 (14) |
| C6 | 0.0362 (19) | 0.037 (2) | 0.038 (2) | −0.0036 (17) | 0.0179 (16) | −0.0003 (16) |
| N2 | 0.0487 (19) | 0.054 (2) | 0.0364 (18) | 0.0079 (16) | 0.0115 (15) | −0.0008 (15) |
| C1 | 0.0372 (19) | 0.039 (2) | 0.036 (2) | −0.0052 (16) | 0.0181 (17) | −0.0005 (16) |
| N5 | 0.0421 (18) | 0.0480 (19) | 0.0379 (18) | 0.0021 (15) | 0.0108 (14) | −0.0026 (15) |
| C3 | 0.057 (3) | 0.058 (3) | 0.038 (2) | −0.015 (2) | 0.020 (2) | −0.0046 (19) |
| N4 | 0.0434 (18) | 0.0510 (19) | 0.0352 (17) | −0.0010 (16) | 0.0073 (14) | −0.0014 (16) |
| N3 | 0.047 (2) | 0.055 (2) | 0.049 (2) | 0.0072 (17) | 0.0154 (17) | −0.0032 (16) |
| C4 | 0.041 (2) | 0.068 (3) | 0.038 (2) | −0.009 (2) | 0.0078 (18) | 0.009 (2) |
| C2 | 0.042 (2) | 0.049 (2) | 0.043 (2) | −0.0064 (18) | 0.0212 (18) | −0.0027 (18) |
| C5 | 0.040 (2) | 0.046 (2) | 0.045 (2) | −0.0021 (17) | 0.0155 (19) | 0.0074 (18) |
| N6 | 0.0382 (18) | 0.049 (2) | 0.0414 (19) | 0.0006 (15) | 0.0156 (15) | −0.0023 (16) |
| O3 | 0.0543 (17) | 0.0578 (17) | 0.0413 (16) | −0.0174 (14) | 0.0136 (13) | −0.0034 (13) |
| O2 | 0.0527 (18) | 0.070 (2) | 0.0460 (17) | −0.0192 (14) | 0.0180 (14) | −0.0189 (14) |
| O1 | 0.077 (2) | 0.080 (2) | 0.0499 (17) | −0.0107 (17) | 0.0314 (16) | 0.0090 (16) |
| N1—C5 | 1.329 (4) | C3—H3 | 0.93 |
| N1—C1 | 1.352 (4) | N4—N3 | 1.318 (4) |
| N1—H1 | 0.86 | N4—H4A | 0.86 |
| C6—N5 | 1.323 (4) | C4—C5 | 1.363 (5) |
| C6—N2 | 1.352 (4) | C4—H4 | 0.93 |
| C6—C1 | 1.446 (5) | C2—H2 | 0.93 |
| N2—N3 | 1.314 (4) | C5—H5 | 0.93 |
| C1—C2 | 1.386 (5) | N6—O1 | 1.228 (3) |
| N5—N4 | 1.318 (4) | N6—O2 | 1.229 (4) |
| C3—C4 | 1.382 (5) | N6—O3 | 1.286 (4) |
| C3—C2 | 1.383 (5) | ||
| C5—N1—C1 | 123.0 (3) | N5—N4—H4A | 122.8 |
| C5—N1—H1 | 118.5 | N3—N4—H4A | 122.8 |
| C1—N1—H1 | 118.5 | N2—N3—N4 | 106.0 (3) |
| N5—C6—N2 | 112.7 (3) | C5—C4—C3 | 118.9 (4) |
| N5—C6—C1 | 124.7 (3) | C5—C4—H4 | 120.5 |
| N2—C6—C1 | 122.6 (3) | C3—C4—H4 | 120.5 |
| N3—N2—C6 | 105.6 (3) | C3—C2—C1 | 119.8 (4) |
| N1—C1—C2 | 117.9 (3) | C3—C2—H2 | 120.1 |
| N1—C1—C6 | 119.3 (3) | C1—C2—H2 | 120.1 |
| C2—C1—C6 | 122.8 (3) | N1—C5—C4 | 120.5 (4) |
| N4—N5—C6 | 101.3 (3) | N1—C5—H5 | 119.8 |
| C4—C3—C2 | 119.8 (4) | C4—C5—H5 | 119.8 |
| C4—C3—H3 | 120.1 | O1—N6—O2 | 122.7 (3) |
| C2—C3—H3 | 120.1 | O1—N6—O3 | 119.3 (3) |
| N5—N4—N3 | 114.4 (3) | O2—N6—O3 | 118.0 (3) |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N1—H1···O3i | 0.86 | 1.92 | 2.772 (4) | 172 |
| N4—H4A···O3 | 0.86 | 1.87 | 2.717 (4) | 170 |
| C2—H2···N2ii | 0.93 | 2.58 | 3.507 (5) | 173 |
| C3—H3···O1iii | 0.93 | 2.52 | 3.435 (5) | 171 |
| C5—H5···O2i | 0.93 | 2.54 | 3.218 (5) | 130 |
| C5—H5···O2iv | 0.93 | 2.36 | 3.223 (5) | 155 |
| Symmetry codes: (i) −x+1/2, y+1/2, −z+3/2; (ii) −x+1/2, −y+1/2, −z+1; (iii) −x+1/2, −y+3/2, −z+1; (iv) x−1/2, −y+5/2, z−1/2. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N1—H1···O3i | 0.86 | 1.92 | 2.772 (4) | 172 |
| N4—H4A···O3 | 0.86 | 1.87 | 2.717 (4) | 170 |
| C2—H2···N2ii | 0.93 | 2.58 | 3.507 (5) | 173 |
| C3—H3···O1iii | 0.93 | 2.52 | 3.435 (5) | 171 |
| C5—H5···O2i | 0.93 | 2.54 | 3.218 (5) | 130 |
| C5—H5···O2iv | 0.93 | 2.36 | 3.223 (5) | 155 |
| Symmetry codes: (i) −x+1/2, y+1/2, −z+3/2; (ii) −x+1/2, −y+1/2, −z+1; (iii) −x+1/2, −y+3/2, −z+1; (iv) x−1/2, −y+5/2, z−1/2. |
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.
Fu, D.-W., Zhang, W. & Xiong, R.-G. (2008). Cryst. Growth Des. 8, 3461–3464.
Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
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.
Wen, X.-C. (2008). Acta Cryst. E64, m768.
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 (Fu et al., 2008; Wang, et al. 2005; Xiong, et al. 2002; Wen 2008). We report here the crystal structure of the title compound, 2-(2H-tetrazol-5-yl)pyridinium nitrate.
In the title compound (Fig.1), the N atom (N1) of the pyridine ring is protonated. The pyridine and tetrazole rings are nearly coplanar and are twisted from each other by a dihedral angle of 8.2 (2)°. The geometric parameters of the tetrazole ring are comparable to those observed in related structures (Wang et al. 2005; Dai & Fu 2008).
The crystal packing is stabilized by N—H···O hydrogen bonds which link the molecules into a helical chain running along the b axis (Table 1 and Fig.2). In addition, C—H···N and C—H···O hydrogen bonds are observed.