Acta Cryst. (2009). E65, o2398 [ doi:10.1107/S1600536809032851 ]
In the cation of the title compound, C6H6N5+·HSO4-, the pyridine and tetrazole rings are close to being co-planar [dihedral angle = 3.98 (7)°]. In the crystal, the ions are linked by O-H
O, N-HO and N-H(O,O) hydrogen bonds, resulting in chains.
Isonicotinonitrile (30 mmol), NaN 3 (45 mmol), NH4Cl (33 mmol) and DMF (50 ml) were added in a flask under nitrogen atmosphere and 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) still 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/H2SO4 (50:1 v/v) solution.
All H atoms attached to C, O and N atoms were fixed geometrically and treated as riding with C–H = 0.93 Å, O–H = 0.82 Å and N–H = 0.86 Å with Uiso(H) =1.2Ueq(C or N) and Uiso(H) =1.5Ueq(O).
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]](./bx2220fig1thm.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]](./bx2220fig2thm.gif)
| Fig. 2. The crystal packing of the title compound showing the two dimensionnal hydrogen bondings network (dashed line). Hydrogen atoms not involved in hydrogen bonding have been omitted for clarity. |
| C6H6N5+·HSO4− | Z = 2 |
| Mr = 245.23 | F(000) = 252 |
| Triclinic, P1 | Dx = 1.708 Mg m−3 |
| Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
| a = 6.6515 (13) Å | Cell parameters from 1961 reflections |
| b = 7.5507 (15) Å | θ = 3.2–27.5° |
| c = 10.072 (2) Å | µ = 0.35 mm−1 |
| α = 77.72 (3)° | T = 298 K |
| β = 76.88 (3)° | Block, colorless |
| γ = 79.71 (3)° | 0.30 × 0.25 × 0.20 mm |
| V = 476.84 (16) Å3 |
| Rigaku Mercury2 diffractometer | 2175 independent reflections |
| Radiation source: fine-focus sealed tube | 1961 reflections with I > 2σ(I) |
| graphite | Rint = 0.055 |
| Detector resolution: 13.6612 pixels mm-1 | θmax = 27.5°, θmin = 3.2° |
| CCD profile fitting scans | h = −8→8 |
| Absorption correction: multi-scan (CrystalClear; Rigaku, 2005) | k = −9→9 |
| Tmin = 0.910, Tmax = 1.000 | l = −13→13 |
| 4917 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)] = 0.050 | H-atom parameters constrained |
| wR(F2) = 0.134 | w = 1/[σ2(Fo2) + (0.0597P)2 + 0.1736P] where P = (Fo2 + 2Fc2)/3 |
| S = 1.07 | (Δ/σ)max < 0.001 |
| 2175 reflections | Δρmax = 0.34 e Å−3 |
| 146 parameters | Δρmin = −0.40 e Å−3 |
| 0 restraints | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
| Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.137 (14) |
| C6H6N5+·HSO4− | γ = 79.71 (3)° |
| Mr = 245.23 | V = 476.84 (16) Å3 |
| Triclinic, P1 | Z = 2 |
| a = 6.6515 (13) Å | Mo Kα radiation |
| b = 7.5507 (15) Å | µ = 0.35 mm−1 |
| c = 10.072 (2) Å | T = 298 K |
| α = 77.72 (3)° | 0.30 × 0.25 × 0.20 mm |
| β = 76.88 (3)° |
| Rigaku Mercury2 diffractometer | 2175 independent reflections |
| Absorption correction: multi-scan (CrystalClear; Rigaku, 2005) | 1961 reflections with I > 2σ(I) |
| Tmin = 0.910, Tmax = 1.000 | Rint = 0.055 |
| 4917 measured reflections | θmax = 27.5° |
| R[F2 > 2σ(F2)] = 0.050 | H-atom parameters constrained |
| wR(F2) = 0.134 | Δρmax = 0.34 e Å−3 |
| S = 1.07 | Δρmin = −0.40 e Å−3 |
| 2175 reflections | Absolute structure: ? |
| 146 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 | ||
| S1 | 0.17610 (8) | 0.76548 (6) | 0.48163 (5) | 0.0345 (2) | |
| O2 | −0.0454 (3) | 0.7896 (2) | 0.54236 (17) | 0.0469 (4) | |
| O1 | 0.2068 (3) | 0.9101 (2) | 0.34498 (15) | 0.0469 (4) | |
| H1B | 0.1631 | 1.0128 | 0.3627 | 0.070* | |
| C6 | 0.2581 (3) | 0.3789 (3) | 0.0215 (2) | 0.0321 (4) | |
| N2 | 0.2528 (3) | 0.5615 (2) | −0.00724 (18) | 0.0394 (4) | |
| O3 | 0.2479 (3) | 0.5928 (2) | 0.43634 (16) | 0.0445 (4) | |
| N1 | 0.2800 (3) | 0.0732 (2) | −0.28273 (19) | 0.0397 (4) | |
| H1A | 0.2824 | 0.0112 | −0.3456 | 0.048* | |
| O4 | 0.3022 (3) | 0.8031 (2) | 0.56937 (19) | 0.0537 (5) | |
| N3 | 0.2423 (3) | 0.6128 (3) | 0.1106 (2) | 0.0438 (5) | |
| N4 | 0.2414 (3) | 0.4632 (3) | 0.20321 (19) | 0.0447 (5) | |
| H4A | 0.2349 | 0.4630 | 0.2895 | 0.054* | |
| N5 | 0.2511 (3) | 0.3125 (3) | 0.15493 (18) | 0.0444 (5) | |
| C2 | 0.2855 (3) | 0.3527 (3) | −0.2218 (2) | 0.0363 (5) | |
| H2 | 0.2935 | 0.4774 | −0.2472 | 0.044* | |
| C3 | 0.2684 (3) | 0.2687 (3) | −0.0841 (2) | 0.0305 (4) | |
| C4 | 0.2597 (3) | 0.0814 (3) | −0.0490 (2) | 0.0374 (5) | |
| H4 | 0.2498 | 0.0217 | 0.0426 | 0.045* | |
| C5 | 0.2661 (4) | −0.0136 (3) | −0.1518 (2) | 0.0415 (5) | |
| H5 | 0.2606 | −0.1389 | −0.1303 | 0.050* | |
| C1 | 0.2904 (4) | 0.2516 (3) | −0.3202 (2) | 0.0395 (5) | |
| H1 | 0.3010 | 0.3072 | −0.4128 | 0.047* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| S1 | 0.0519 (4) | 0.0259 (3) | 0.0276 (3) | −0.0071 (2) | −0.0060 (2) | −0.00971 (19) |
| O2 | 0.0546 (10) | 0.0378 (8) | 0.0457 (9) | −0.0136 (7) | 0.0045 (7) | −0.0116 (7) |
| O1 | 0.0696 (11) | 0.0312 (8) | 0.0346 (8) | −0.0076 (7) | 0.0002 (7) | −0.0046 (6) |
| C6 | 0.0385 (10) | 0.0295 (9) | 0.0286 (9) | −0.0064 (8) | −0.0048 (7) | −0.0064 (7) |
| N2 | 0.0534 (11) | 0.0322 (9) | 0.0353 (9) | −0.0087 (8) | −0.0078 (8) | −0.0105 (7) |
| O3 | 0.0711 (11) | 0.0288 (8) | 0.0365 (8) | −0.0053 (7) | −0.0095 (7) | −0.0146 (6) |
| N1 | 0.0495 (10) | 0.0379 (10) | 0.0384 (10) | −0.0063 (8) | −0.0112 (8) | −0.0181 (8) |
| O4 | 0.0735 (12) | 0.0439 (9) | 0.0561 (10) | −0.0003 (8) | −0.0281 (9) | −0.0259 (8) |
| N3 | 0.0573 (11) | 0.0383 (10) | 0.0399 (10) | −0.0082 (8) | −0.0081 (8) | −0.0160 (8) |
| N4 | 0.0634 (13) | 0.0434 (10) | 0.0290 (9) | −0.0042 (9) | −0.0081 (8) | −0.0141 (7) |
| N5 | 0.0654 (13) | 0.0396 (10) | 0.0284 (9) | −0.0074 (9) | −0.0058 (8) | −0.0099 (7) |
| C2 | 0.0487 (12) | 0.0312 (10) | 0.0309 (10) | −0.0111 (9) | −0.0078 (8) | −0.0052 (8) |
| C3 | 0.0349 (9) | 0.0283 (9) | 0.0304 (9) | −0.0050 (7) | −0.0076 (7) | −0.0082 (7) |
| C4 | 0.0495 (12) | 0.0300 (10) | 0.0335 (10) | −0.0082 (9) | −0.0098 (8) | −0.0032 (8) |
| C5 | 0.0549 (13) | 0.0261 (10) | 0.0462 (12) | −0.0066 (9) | −0.0130 (10) | −0.0080 (8) |
| C1 | 0.0524 (12) | 0.0380 (11) | 0.0305 (10) | −0.0098 (9) | −0.0101 (9) | −0.0062 (8) |
| S1—O3 | 1.4378 (15) | N3—N4 | 1.302 (3) |
| S1—O4 | 1.4469 (17) | N4—N5 | 1.315 (3) |
| S1—O2 | 1.4564 (17) | N4—H4A | 0.8600 |
| S1—O1 | 1.5623 (16) | C2—C1 | 1.365 (3) |
| O1—H1B | 0.8200 | C2—C3 | 1.385 (3) |
| C6—N5 | 1.324 (3) | C2—H2 | 0.9300 |
| C6—N2 | 1.343 (3) | C3—C4 | 1.392 (3) |
| C6—C3 | 1.466 (3) | C4—C5 | 1.369 (3) |
| N2—N3 | 1.309 (2) | C4—H4 | 0.9300 |
| N1—C1 | 1.329 (3) | C5—H5 | 0.9300 |
| N1—C5 | 1.332 (3) | C1—H1 | 0.9300 |
| N1—H1A | 0.8600 | ||
| O3—S1—O4 | 112.84 (10) | N5—N4—H4A | 122.5 |
| O3—S1—O2 | 113.35 (10) | N4—N5—C6 | 100.98 (18) |
| O4—S1—O2 | 112.29 (11) | C1—C2—C3 | 119.79 (19) |
| O3—S1—O1 | 104.09 (9) | C1—C2—H2 | 120.1 |
| O4—S1—O1 | 106.97 (11) | C3—C2—H2 | 120.1 |
| O2—S1—O1 | 106.53 (10) | C2—C3—C4 | 119.02 (18) |
| S1—O1—H1B | 109.5 | C2—C3—C6 | 119.51 (18) |
| N5—C6—N2 | 112.09 (18) | C4—C3—C6 | 121.47 (18) |
| N5—C6—C3 | 124.79 (18) | C5—C4—C3 | 118.83 (19) |
| N2—C6—C3 | 123.12 (18) | C5—C4—H4 | 120.6 |
| N3—N2—C6 | 106.28 (18) | C3—C4—H4 | 120.6 |
| C1—N1—C5 | 122.79 (18) | N1—C5—C4 | 120.08 (19) |
| C1—N1—H1A | 118.6 | N1—C5—H5 | 120.0 |
| C5—N1—H1A | 118.6 | C4—C5—H5 | 120.0 |
| N4—N3—N2 | 105.63 (17) | N1—C1—C2 | 119.5 (2) |
| N3—N4—N5 | 115.02 (17) | N1—C1—H1 | 120.3 |
| N3—N4—H4A | 122.5 | C2—C1—H1 | 120.3 |
| C6—N2—N3—N4 | −0.1 (2) | C3—C4—C5—N1 | −0.1 (3) |
| N2—N3—N4—N5 | 0.1 (3) | N4—N5—C6—N2 | 0.0 (2) |
| N3—N4—N5—C6 | −0.1 (3) | N4—N5—C6—C3 | −179.4 (2) |
| C5—N1—C1—C2 | −0.4 (3) | N3—N2—C6—N5 | 0.0 (2) |
| N1—C1—C2—C3 | −0.4 (3) | N3—N2—C6—C3 | 179.51 (19) |
| C1—C2—C3—C4 | 0.9 (3) | C2—C3—C6—N5 | −176.8 (2) |
| C1—C2—C3—C6 | −178.5 (2) | C4—C3—C6—N5 | 3.8 (3) |
| C2—C3—C4—C5 | −0.7 (3) | C2—C3—C6—N2 | 3.7 (3) |
| C6—C3—C4—C5 | 178.7 (2) | C4—C3—C6—N2 | −175.68 (19) |
| C1—N1—C5—C4 | 0.7 (3) |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O1—H1B···O2i | 0.82 | 1.90 | 2.694 (2) | 163 |
| N1—H1A···O4ii | 0.86 | 1.91 | 2.736 (2) | 159 |
| N4—H4A···O2iii | 0.86 | 2.57 | 3.033 (3) | 115 |
| N4—H4A···O3 | 0.86 | 1.97 | 2.741 (2) | 150 |
| Symmetry codes: (i) −x, −y+2, −z+1; (ii) x, y−1, z−1; (iii) −x, −y+1, −z+1. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O1—H1B···O2i | 0.82 | 1.90 | 2.694 (2) | 163 |
| N1—H1A···O4ii | 0.86 | 1.91 | 2.736 (2) | 159 |
| N4—H4A···O2iii | 0.86 | 2.57 | 3.033 (3) | 115 |
| N4—H4A···O3 | 0.86 | 1.97 | 2.741 (2) | 150 |
| Symmetry codes: (i) −x, −y+2, −z+1; (ii) x, y−1, z−1; (iii) −x, −y+1, −z+1. |
This work was supported by a start-up grant from Southeast University to Professor Ren-Gen Xiong.
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The construction of metal-organic coordination compounds has attracted much attention owing to the potential functions, such as permittivity, fluorescence, magnetism and optical properties. (Fu et al., 2007; Huang et al., 1999; Liu et al., 1999; Xie et al., 2003; Zhang et al.,2001; Zhang et al.,2000) Tetrazole compounds are a class of excellent ligands for the construction of novel metal-organic frameworks, because of its various coordination modes. (Wang, et al. 2005; Fu et al., 2008). We report here the crystal and molecular structure of the title compound, 4-(2H-tetrazol-5-yl)pyridinium bisulfate), (I) , Fig.1, The pyridine N atoms are protonated. The pyridine and tetrazole rings are nearly coplanar and only twisted from each other by a dihedral angle of 3.98 (7) °. The geometric parameters of the tetrazole rings are comparable to those in related molecules (Wang, et al. 2005; Fu et al., 2008).The crystal packing is stabilized by coulombic forces , one O—H···O and three N—H···O hydrogen bonds (Table 1 and Fig.2).