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Acta Crystallogr Sect E Struct Rep Online. 2009 June 1; 65(Pt 6): o1318.
Published online 2009 May 20. doi:  10.1107/S1600536809018078
PMCID: PMC2969575

2-(2H-Tetra­zol-5-yl)pyridinium nitrate

Abstract

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—H(...)N and C—H(...)O hydrogen bonds are also observed.

Related literature

For the use of tetra­zole derivatives in coordination chemistry, see: Xiong et al. (2002 [triangle]); Fu et al. (2008 [triangle]); Wang et al. (2005 [triangle]). For the crystal structures of related compounds, see: Dai & Fu (2008 [triangle]); Wen (2008 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-65-o1318-scheme1.jpg

Experimental

Crystal data

  • C6H6N5 +·NO3
  • M r = 210.17
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-o1318-efi1.jpg
  • a = 20.400 (4) Å
  • b = 4.8981 (10) Å
  • c = 19.135 (4) Å
  • β = 114.77 (3)°
  • V = 1736.1 (7) Å3
  • Z = 8
  • Mo Kα radiation
  • μ = 0.13 mm−1
  • T = 298 K
  • 0.20 × 0.15 × 0.15 mm

Data collection

  • Rigaku Mercury2 diffractometer
  • Absorption correction: multi-scan (CrystalClear, Rigaku, 2005 [triangle]) T min = 0.976, T max = 0.980
  • 8427 measured reflections
  • 1999 independent reflections
  • 1033 reflections with I > 2σ(I)
  • R int = 0.123

Refinement

  • R[F 2 > 2σ(F 2)] = 0.081
  • wR(F 2) = 0.209
  • S = 1.04
  • 1999 reflections
  • 136 parameters
  • H-atom parameters constrained
  • Δρmax = 0.34 e Å−3
  • Δρmin = −0.36 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/S1600536809018078/ci2780sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809018078/ci2780Isup2.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

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.

Experimental

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.

Refinement

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).

Figures

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

Crystal data

C6H6N5+·NO3F(000) = 864
Mr = 210.17Dx = 1.608 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 1999 reflections
a = 20.400 (4) Åθ = 3.8–27.5°
b = 4.8981 (10) ŵ = 0.13 mm1
c = 19.135 (4) ÅT = 298 K
β = 114.77 (3)°Block, colourless
V = 1736.1 (7) Å30.20 × 0.15 × 0.15 mm
Z = 8

Data collection

Rigaku Mercury2 diffractometer1999 independent reflections
Radiation source: fine-focus sealed tube1033 reflections with I > 2σ(I)
graphiteRint = 0.123
Detector resolution: 13.6612 pixels mm-1θmax = 27.5°, θmin = 3.8°
ω scansh = −26→26
Absorption correction: multi-scan (CrystalClear, Rigaku, 2005)k = −6→6
Tmin = 0.976, Tmax = 0.980l = −24→24
8427 measured reflections

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.081Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.209H-atom parameters constrained
S = 1.04w = 1/[σ2(Fo2) + (0.0838P)2] where P = (Fo2 + 2Fc2)/3
1999 reflections(Δ/σ)max = 0.001
136 parametersΔρmax = 0.34 e Å3
0 restraintsΔρmin = −0.36 e Å3

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
N10.11658 (15)0.9420 (6)0.51774 (16)0.0383 (7)
H10.12391.00550.56230.046*
C60.21176 (18)0.6182 (7)0.58420 (19)0.0362 (8)
N20.24979 (17)0.3908 (6)0.58539 (17)0.0485 (8)
C10.15732 (18)0.7297 (7)0.51387 (19)0.0364 (8)
N50.23230 (16)0.7307 (6)0.65302 (17)0.0447 (8)
C30.0917 (2)0.7442 (8)0.3768 (2)0.0506 (10)
H30.08310.67710.32830.061*
N40.28398 (16)0.5624 (6)0.69580 (17)0.0463 (8)
H4A0.30820.58460.74450.056*
N30.29538 (17)0.3572 (7)0.65769 (18)0.0518 (9)
C40.0518 (2)0.9615 (9)0.3841 (2)0.0520 (11)
H40.01611.04110.34080.062*
C20.14442 (19)0.6270 (8)0.4418 (2)0.0436 (9)
H20.17110.47980.43710.052*
C50.0657 (2)1.0571 (8)0.4558 (2)0.0446 (9)
H50.03951.20390.46150.053*
N60.41263 (16)0.8821 (6)0.85439 (18)0.0434 (8)
O30.37035 (14)0.6773 (5)0.84530 (13)0.0533 (8)
O20.44457 (14)0.9758 (6)0.91958 (15)0.0570 (8)
O10.41958 (16)0.9759 (6)0.79835 (16)0.0672 (9)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
N10.0387 (17)0.0438 (18)0.0341 (16)−0.0043 (14)0.0169 (14)−0.0018 (14)
C60.0362 (19)0.037 (2)0.038 (2)−0.0036 (17)0.0179 (16)−0.0003 (16)
N20.0487 (19)0.054 (2)0.0364 (18)0.0079 (16)0.0115 (15)−0.0008 (15)
C10.0372 (19)0.039 (2)0.036 (2)−0.0052 (16)0.0181 (17)−0.0005 (16)
N50.0421 (18)0.0480 (19)0.0379 (18)0.0021 (15)0.0108 (14)−0.0026 (15)
C30.057 (3)0.058 (3)0.038 (2)−0.015 (2)0.020 (2)−0.0046 (19)
N40.0434 (18)0.0510 (19)0.0352 (17)−0.0010 (16)0.0073 (14)−0.0014 (16)
N30.047 (2)0.055 (2)0.049 (2)0.0072 (17)0.0154 (17)−0.0032 (16)
C40.041 (2)0.068 (3)0.038 (2)−0.009 (2)0.0078 (18)0.009 (2)
C20.042 (2)0.049 (2)0.043 (2)−0.0064 (18)0.0212 (18)−0.0027 (18)
C50.040 (2)0.046 (2)0.045 (2)−0.0021 (17)0.0155 (19)0.0074 (18)
N60.0382 (18)0.049 (2)0.0414 (19)0.0006 (15)0.0156 (15)−0.0023 (16)
O30.0543 (17)0.0578 (17)0.0413 (16)−0.0174 (14)0.0136 (13)−0.0034 (13)
O20.0527 (18)0.070 (2)0.0460 (17)−0.0192 (14)0.0180 (14)−0.0189 (14)
O10.077 (2)0.080 (2)0.0499 (17)−0.0107 (17)0.0314 (16)0.0090 (16)

Geometric parameters (Å, °)

N1—C51.329 (4)C3—H30.93
N1—C11.352 (4)N4—N31.318 (4)
N1—H10.86N4—H4A0.86
C6—N51.323 (4)C4—C51.363 (5)
C6—N21.352 (4)C4—H40.93
C6—C11.446 (5)C2—H20.93
N2—N31.314 (4)C5—H50.93
C1—C21.386 (5)N6—O11.228 (3)
N5—N41.318 (4)N6—O21.229 (4)
C3—C41.382 (5)N6—O31.286 (4)
C3—C21.383 (5)
C5—N1—C1123.0 (3)N5—N4—H4A122.8
C5—N1—H1118.5N3—N4—H4A122.8
C1—N1—H1118.5N2—N3—N4106.0 (3)
N5—C6—N2112.7 (3)C5—C4—C3118.9 (4)
N5—C6—C1124.7 (3)C5—C4—H4120.5
N2—C6—C1122.6 (3)C3—C4—H4120.5
N3—N2—C6105.6 (3)C3—C2—C1119.8 (4)
N1—C1—C2117.9 (3)C3—C2—H2120.1
N1—C1—C6119.3 (3)C1—C2—H2120.1
C2—C1—C6122.8 (3)N1—C5—C4120.5 (4)
N4—N5—C6101.3 (3)N1—C5—H5119.8
C4—C3—C2119.8 (4)C4—C5—H5119.8
C4—C3—H3120.1O1—N6—O2122.7 (3)
C2—C3—H3120.1O1—N6—O3119.3 (3)
N5—N4—N3114.4 (3)O2—N6—O3118.0 (3)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1···O3i0.861.922.772 (4)172
N4—H4A···O30.861.872.717 (4)170
C2—H2···N2ii0.932.583.507 (5)173
C3—H3···O1iii0.932.523.435 (5)171
C5—H5···O2i0.932.543.218 (5)130
C5—H5···O2iv0.932.363.223 (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.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: CI2780).

References

  • Dai, W. & Fu, D.-W. (2008). Acta Cryst. E64, o1444. [PMC free article] [PubMed]
  • 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. [PubMed]
  • 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. [PubMed]
  • Wen, X.-C. (2008). Acta Cryst. E64, m768. [PMC free article] [PubMed]
  • Xiong, R.-G., Xue, X., Zhao, H., You, X.-Z., Abrahams, B. F. & Xue, Z.-L. (2002). Angew. Chem. Int. Ed.41, 3800–3803. [PubMed]

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