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Acta Crystallogr Sect E Struct Rep Online. 2009 October 1; 65(Pt 10): o2398.
Published online 2009 September 9. doi:  10.1107/S1600536809032851
PMCID: PMC2970296

4-(2H-Tetra­zol-5-yl)pyridinium hydrogen sulfate

Abstract

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—H(...)O and N—H(...)(O,O) hydrogen bonds, resulting in chains.

Related literature

Tetrazoles are excellent ligands for the construction of metal-organic frameworks because of their various coordination modes, see: Fu et al. (2008 [triangle]); Wang et al. (2005 [triangle]). For the applications of metal-organic coordination compounds, see: Fu et al. (2007 [triangle]); Huang et al. (1999 [triangle]); Liu et al. (1999 [triangle]); Xie et al. (2003 [triangle]); Zhang et al. (2001 [triangle]); Zhang et al. (2000 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-65-o2398-scheme1.jpg

Experimental

Crystal data

  • C6H6N5 +·HSO4
  • M r = 245.23
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-o2398-efi1.jpg
  • a = 6.6515 (13) Å
  • b = 7.5507 (15) Å
  • c = 10.072 (2) Å
  • α = 77.72 (3)°
  • β = 76.88 (3)°
  • γ = 79.71 (3)°
  • V = 476.84 (16) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 0.35 mm−1
  • T = 298 K
  • 0.30 × 0.25 × 0.20 mm

Data collection

  • Rigaku Mercury2 diffractometer
  • Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 [triangle]) T min = 0.910, T max = 1.000 (expected range = 0.848–0.932)
  • 4917 measured reflections
  • 2175 independent reflections
  • 1961 reflections with I > 2σ(I)
  • R int = 0.055

Refinement

  • R[F 2 > 2σ(F 2)] = 0.050
  • wR(F 2) = 0.134
  • S = 1.07
  • 2175 reflections
  • 146 parameters
  • H-atom parameters constrained
  • Δρmax = 0.34 e Å−3
  • Δρmin = −0.41 e Å−3

Data collection: CrystalClear (Rigaku, 2005 [triangle]); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXTL.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809032851/bx2220sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809032851/bx2220Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

This work was supported by a start-up grant from Southeast University to Professor Ren-Gen Xiong.

supplementary crystallographic information

Comment

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).

Experimental

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.

Refinement

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).

Figures

Fig. 1.
A view of the title compound with the atomic numbering scheme. Displacement ellipsoids were drawn at the 30% probability level.
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.

Crystal data

C6H6N5+·HSO4Z = 2
Mr = 245.23F(000) = 252
Triclinic, P1Dx = 1.708 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 6.6515 (13) ÅCell parameters from 1961 reflections
b = 7.5507 (15) Åθ = 3.2–27.5°
c = 10.072 (2) ŵ = 0.35 mm1
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

Data collection

Rigaku Mercury2 diffractometer2175 independent reflections
Radiation source: fine-focus sealed tube1961 reflections with I > 2σ(I)
graphiteRint = 0.055
Detector resolution: 13.6612 pixels mm-1θmax = 27.5°, θmin = 3.2°
CCD profile fitting scansh = −8→8
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)k = −9→9
Tmin = 0.910, Tmax = 1.000l = −13→13
4917 measured reflections

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.050H-atom parameters constrained
wR(F2) = 0.134w = 1/[σ2(Fo2) + (0.0597P)2 + 0.1736P] where P = (Fo2 + 2Fc2)/3
S = 1.07(Δ/σ)max < 0.001
2175 reflectionsΔρmax = 0.34 e Å3
146 parametersΔρmin = −0.40 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.137 (14)

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

xyzUiso*/Ueq
S10.17610 (8)0.76548 (6)0.48163 (5)0.0345 (2)
O2−0.0454 (3)0.7896 (2)0.54236 (17)0.0469 (4)
O10.2068 (3)0.9101 (2)0.34498 (15)0.0469 (4)
H1B0.16311.01280.36270.070*
C60.2581 (3)0.3789 (3)0.0215 (2)0.0321 (4)
N20.2528 (3)0.5615 (2)−0.00724 (18)0.0394 (4)
O30.2479 (3)0.5928 (2)0.43634 (16)0.0445 (4)
N10.2800 (3)0.0732 (2)−0.28273 (19)0.0397 (4)
H1A0.28240.0112−0.34560.048*
O40.3022 (3)0.8031 (2)0.56937 (19)0.0537 (5)
N30.2423 (3)0.6128 (3)0.1106 (2)0.0438 (5)
N40.2414 (3)0.4632 (3)0.20321 (19)0.0447 (5)
H4A0.23490.46300.28950.054*
N50.2511 (3)0.3125 (3)0.15493 (18)0.0444 (5)
C20.2855 (3)0.3527 (3)−0.2218 (2)0.0363 (5)
H20.29350.4774−0.24720.044*
C30.2684 (3)0.2687 (3)−0.0841 (2)0.0305 (4)
C40.2597 (3)0.0814 (3)−0.0490 (2)0.0374 (5)
H40.24980.02170.04260.045*
C50.2661 (4)−0.0136 (3)−0.1518 (2)0.0415 (5)
H50.2606−0.1389−0.13030.050*
C10.2904 (4)0.2516 (3)−0.3202 (2)0.0395 (5)
H10.30100.3072−0.41280.047*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
S10.0519 (4)0.0259 (3)0.0276 (3)−0.0071 (2)−0.0060 (2)−0.00971 (19)
O20.0546 (10)0.0378 (8)0.0457 (9)−0.0136 (7)0.0045 (7)−0.0116 (7)
O10.0696 (11)0.0312 (8)0.0346 (8)−0.0076 (7)0.0002 (7)−0.0046 (6)
C60.0385 (10)0.0295 (9)0.0286 (9)−0.0064 (8)−0.0048 (7)−0.0064 (7)
N20.0534 (11)0.0322 (9)0.0353 (9)−0.0087 (8)−0.0078 (8)−0.0105 (7)
O30.0711 (11)0.0288 (8)0.0365 (8)−0.0053 (7)−0.0095 (7)−0.0146 (6)
N10.0495 (10)0.0379 (10)0.0384 (10)−0.0063 (8)−0.0112 (8)−0.0181 (8)
O40.0735 (12)0.0439 (9)0.0561 (10)−0.0003 (8)−0.0281 (9)−0.0259 (8)
N30.0573 (11)0.0383 (10)0.0399 (10)−0.0082 (8)−0.0081 (8)−0.0160 (8)
N40.0634 (13)0.0434 (10)0.0290 (9)−0.0042 (9)−0.0081 (8)−0.0141 (7)
N50.0654 (13)0.0396 (10)0.0284 (9)−0.0074 (9)−0.0058 (8)−0.0099 (7)
C20.0487 (12)0.0312 (10)0.0309 (10)−0.0111 (9)−0.0078 (8)−0.0052 (8)
C30.0349 (9)0.0283 (9)0.0304 (9)−0.0050 (7)−0.0076 (7)−0.0082 (7)
C40.0495 (12)0.0300 (10)0.0335 (10)−0.0082 (9)−0.0098 (8)−0.0032 (8)
C50.0549 (13)0.0261 (10)0.0462 (12)−0.0066 (9)−0.0130 (10)−0.0080 (8)
C10.0524 (12)0.0380 (11)0.0305 (10)−0.0098 (9)−0.0101 (9)−0.0062 (8)

Geometric parameters (Å, °)

S1—O31.4378 (15)N3—N41.302 (3)
S1—O41.4469 (17)N4—N51.315 (3)
S1—O21.4564 (17)N4—H4A0.8600
S1—O11.5623 (16)C2—C11.365 (3)
O1—H1B0.8200C2—C31.385 (3)
C6—N51.324 (3)C2—H20.9300
C6—N21.343 (3)C3—C41.392 (3)
C6—C31.466 (3)C4—C51.369 (3)
N2—N31.309 (2)C4—H40.9300
N1—C11.329 (3)C5—H50.9300
N1—C51.332 (3)C1—H10.9300
N1—H1A0.8600
O3—S1—O4112.84 (10)N5—N4—H4A122.5
O3—S1—O2113.35 (10)N4—N5—C6100.98 (18)
O4—S1—O2112.29 (11)C1—C2—C3119.79 (19)
O3—S1—O1104.09 (9)C1—C2—H2120.1
O4—S1—O1106.97 (11)C3—C2—H2120.1
O2—S1—O1106.53 (10)C2—C3—C4119.02 (18)
S1—O1—H1B109.5C2—C3—C6119.51 (18)
N5—C6—N2112.09 (18)C4—C3—C6121.47 (18)
N5—C6—C3124.79 (18)C5—C4—C3118.83 (19)
N2—C6—C3123.12 (18)C5—C4—H4120.6
N3—N2—C6106.28 (18)C3—C4—H4120.6
C1—N1—C5122.79 (18)N1—C5—C4120.08 (19)
C1—N1—H1A118.6N1—C5—H5120.0
C5—N1—H1A118.6C4—C5—H5120.0
N4—N3—N2105.63 (17)N1—C1—C2119.5 (2)
N3—N4—N5115.02 (17)N1—C1—H1120.3
N3—N4—H4A122.5C2—C1—H1120.3
C6—N2—N3—N4−0.1 (2)C3—C4—C5—N1−0.1 (3)
N2—N3—N4—N50.1 (3)N4—N5—C6—N20.0 (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—N50.0 (2)
N1—C1—C2—C3−0.4 (3)N3—N2—C6—C3179.51 (19)
C1—C2—C3—C40.9 (3)C2—C3—C6—N5−176.8 (2)
C1—C2—C3—C6−178.5 (2)C4—C3—C6—N53.8 (3)
C2—C3—C4—C5−0.7 (3)C2—C3—C6—N23.7 (3)
C6—C3—C4—C5178.7 (2)C4—C3—C6—N2−175.68 (19)
C1—N1—C5—C40.7 (3)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O1—H1B···O2i0.821.902.694 (2)163
N1—H1A···O4ii0.861.912.736 (2)159
N4—H4A···O2iii0.862.573.033 (3)115
N4—H4A···O30.861.972.741 (2)150

Symmetry codes: (i) −x, −y+2, −z+1; (ii) x, y−1, z−1; (iii) −x, −y+1, −z+1.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: BX2220).

References

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