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Acta Crystallogr Sect E Struct Rep Online. 2008 October 1; 64(Pt 10): o2028.
Published online 2008 September 27. doi:  10.1107/S1600536808030791
PMCID: PMC2959428

2-Amino-5-(1H-tetra­zol-5-yl)pyridin-1-ium nitrate

Abstract

In the cation of the title compound, C6H7N6 +·NO3 , the pyridine and tetra­zole rings are essentially coplanar, exhibiting a dihedral angle of 6.30 (6)°. In the crystal structure, N—H(...)O, N—H(...)N, C—H(...)O and C—H(...)N hydrogen bonds form a three-dimensional network.

Related literature

For general background on the chemistry of tetra­zole derivatives, see: Dunica et al. (1991 [triangle]); Wittenberger & Donner (1993 [triangle]); Zou et al. (2007 [triangle]); Xiong et al. (2002 [triangle]). For the crystal structures of related compounds, see: Dai & Fu (2008 [triangle]); Wang et al. (2005 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-64-o2028-scheme1.jpg

Experimental

Crystal data

  • C6H7N6 +·NO3
  • M r = 225.19
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-o2028-efi1.jpg
  • a = 8.3797 (17) Å
  • b = 6.9314 (14) Å
  • c = 15.881 (3) Å
  • β = 94.31 (3)°
  • V = 919.8 (3) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.13 mm−1
  • T = 298 (2) K
  • 0.30 × 0.22 × 0.20 mm

Data collection

  • Rigaku Mercury2 diffractometer
  • Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 [triangle]) T min = 0.916, T max = 0.970
  • 8766 measured reflections
  • 2023 independent reflections
  • 1520 reflections with I > 2σ(I)
  • R int = 0.041

Refinement

  • R[F 2 > 2σ(F 2)] = 0.049
  • wR(F 2) = 0.120
  • S = 1.07
  • 2023 reflections
  • 173 parameters
  • All H-atom parameters refined
  • Δρmax = 0.15 e Å−3
  • Δρmin = −0.18 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/PC (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXTL/PC.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808030791/rz2247sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808030791/rz2247Isup2.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 R.-G. Xiong.

supplementary crystallographic information

Comment

The tetrazole functional group has found a wide range of applications in coordination chemistry as ligand, in medicinal chemistry as a metabolically stable surrogate for the carboxylic acid group, and in materials science as high density energy material (Wang et al., 2005; Xiong et al., 2002; Zou et al., 2007; Dunica et al., 1991; Wittenberger & Donner, 1993). We report here the crystal structure of the title compound, 5-(1H-tetrazol-5-yl)pyridin-2-amine-1-ium nitrate.

In the cation of the title compound (Fig. 1) the pyridine and tetrazole rings are essentially coplanar with a dihedral angle of only 6.30 (6)°. Bond distances and angles of the tetrazole ring are within the usual range (Wang et al., 2005; Dai & Fu, 2008). The pyridine N atom is protonated. The crystal packing is consolidated by N—H···O, N—H···N, C—H···O and C—H···N hydrogen bonds to form a three-dimentional network. (Table 1, Fig. 2).

Experimental

2-Amino-5-cyanopyridine (30 mmol), NaN3 (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 nitrate acid (6 M) till 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/nitric acid (50:1 v/v) solution.

Refinement

All H atoms were located in difference Fourier maps and refined freely.

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 viewed along the b axis showing the three-dimensionnal hydrogen bonding network (dashed lines). Hydrogen atoms not involved in hydrogen bonding are omitted for clarity.

Crystal data

C6H7N6+·NO3F(000) = 464
Mr = 225.19Dx = 1.626 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 1772 reflections
a = 8.3797 (17) Åθ = 2.4–27.1°
b = 6.9314 (14) ŵ = 0.13 mm1
c = 15.881 (3) ÅT = 298 K
β = 94.31 (3)°Block, colourless
V = 919.8 (3) Å30.30 × 0.22 × 0.20 mm
Z = 4

Data collection

Rigaku Mercury2 (2x2 bin mode) diffractometer2023 independent reflections
Radiation source: fine-focus sealed tube1520 reflections with I > 2σ(I)
graphiteRint = 0.041
Detector resolution: 13.6612 pixels mm-1θmax = 27.1°, θmin = 3.2°
ω scansh = −10→10
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)k = −8→8
Tmin = 0.916, Tmax = 0.970l = −20→20
8766 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)] = 0.049Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.120All H-atom parameters refined
S = 1.07w = 1/[σ2(Fo2) + (0.0527P)2 + 0.2064P] where P = (Fo2 + 2Fc2)/3
2023 reflections(Δ/σ)max < 0.001
173 parametersΔρmax = 0.15 e Å3
0 restraintsΔρmin = −0.18 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
O10.49052 (18)0.0891 (2)0.58329 (9)0.0552 (4)
O20.3288 (2)0.0420 (2)0.68089 (9)0.0632 (5)
O30.46287 (18)0.3054 (2)0.67890 (10)0.0588 (4)
N70.42643 (19)0.1424 (2)0.64808 (10)0.0406 (4)
N10.2311 (2)0.0535 (2)0.27752 (10)0.0416 (4)
C20.2037 (2)0.2485 (3)0.40803 (11)0.0359 (4)
C50.2593 (2)0.5628 (3)0.51712 (11)0.0401 (4)
N50.3153 (2)0.5556 (2)0.43967 (10)0.0427 (4)
C40.1695 (2)0.4035 (3)0.54193 (12)0.0411 (5)
C60.1714 (2)0.0831 (3)0.35207 (11)0.0367 (4)
N40.0781 (2)−0.0636 (3)0.36762 (11)0.0526 (5)
N60.2911 (3)0.7171 (3)0.56527 (13)0.0550 (5)
C30.1443 (2)0.2500 (3)0.48954 (12)0.0399 (4)
N20.1724 (2)−0.1144 (2)0.24520 (10)0.0497 (5)
C10.2875 (2)0.4049 (3)0.38512 (12)0.0414 (5)
N30.0808 (2)−0.1835 (3)0.29971 (11)0.0577 (5)
H6A0.345 (3)0.815 (4)0.5462 (15)0.066 (8)*
H6B0.260 (4)0.723 (4)0.618 (2)0.092 (10)*
H1A0.306 (3)0.126 (3)0.2484 (15)0.066 (7)*
H40.132 (2)0.408 (3)0.5949 (13)0.045 (5)*
H30.085 (3)0.143 (3)0.5074 (13)0.052 (6)*
H10.325 (3)0.423 (3)0.3298 (14)0.056 (6)*
H50.370 (3)0.658 (3)0.4211 (14)0.061 (7)*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O10.0669 (10)0.0599 (10)0.0416 (8)0.0075 (8)0.0238 (7)−0.0058 (7)
O20.0879 (12)0.0556 (9)0.0497 (9)−0.0239 (9)0.0292 (9)−0.0047 (7)
O30.0629 (10)0.0531 (9)0.0633 (10)−0.0168 (8)0.0236 (8)−0.0186 (7)
N70.0451 (9)0.0430 (9)0.0345 (8)0.0031 (7)0.0084 (7)−0.0002 (7)
N10.0519 (10)0.0426 (9)0.0314 (8)−0.0025 (8)0.0094 (7)0.0003 (7)
C20.0373 (10)0.0387 (10)0.0321 (9)−0.0009 (8)0.0055 (7)0.0016 (8)
C50.0445 (10)0.0413 (11)0.0344 (9)0.0030 (8)0.0015 (8)−0.0005 (8)
N50.0499 (10)0.0397 (9)0.0391 (9)−0.0064 (8)0.0081 (8)0.0028 (7)
C40.0457 (11)0.0481 (11)0.0302 (9)−0.0006 (9)0.0077 (8)0.0010 (8)
C60.0395 (10)0.0406 (10)0.0306 (9)−0.0012 (8)0.0063 (8)0.0029 (7)
N40.0623 (11)0.0533 (11)0.0440 (10)−0.0183 (9)0.0154 (9)−0.0049 (8)
N60.0739 (14)0.0439 (11)0.0475 (11)−0.0070 (10)0.0060 (10)−0.0057 (9)
C30.0414 (10)0.0445 (11)0.0344 (10)−0.0052 (9)0.0076 (8)0.0037 (8)
N20.0650 (11)0.0454 (10)0.0392 (9)−0.0052 (9)0.0077 (8)−0.0030 (8)
C10.0469 (11)0.0453 (11)0.0331 (10)−0.0040 (9)0.0101 (8)0.0021 (8)
N30.0750 (13)0.0515 (11)0.0475 (10)−0.0159 (10)0.0118 (9)−0.0056 (8)

Geometric parameters (Å, °)

O1—N71.2517 (19)N5—C11.366 (2)
O2—N71.221 (2)N5—H50.91 (2)
O3—N71.260 (2)C4—C31.358 (3)
N1—C61.336 (2)C4—H40.92 (2)
N1—N21.350 (2)C6—N41.317 (2)
N1—H1A0.95 (2)N4—N31.363 (2)
C2—C11.356 (3)N6—H6A0.88 (3)
C2—C31.422 (2)N6—H6B0.90 (3)
C2—C61.463 (3)C3—H30.95 (2)
C5—N61.330 (3)N2—N31.292 (2)
C5—N51.350 (2)C1—H10.96 (2)
C5—C41.409 (3)
O2—N7—O1121.71 (17)C5—C4—H4117.3 (12)
O2—N7—O3119.76 (16)N4—C6—N1108.35 (17)
O1—N7—O3118.53 (16)N4—C6—C2125.21 (16)
C6—N1—N2108.63 (16)N1—C6—C2126.44 (17)
C6—N1—H1A131.0 (14)C6—N4—N3106.09 (16)
N2—N1—H1A120.3 (14)C5—N6—H6A120.5 (16)
C1—C2—C3117.54 (18)C5—N6—H6B120.9 (19)
C1—C2—C6122.64 (16)H6A—N6—H6B119 (2)
C3—C2—C6119.82 (17)C4—C3—C2120.98 (18)
N6—C5—N5119.03 (19)C4—C3—H3119.4 (13)
N6—C5—C4123.88 (19)C2—C3—H3119.6 (13)
N5—C5—C4117.09 (17)N3—N2—N1106.44 (16)
C5—N5—C1123.48 (17)C2—C1—N5120.56 (17)
C5—N5—H5119.1 (15)C2—C1—H1123.9 (13)
C1—N5—H5117.4 (15)N5—C1—H1115.4 (13)
C3—C4—C5120.32 (18)N2—N3—N4110.49 (17)
C3—C4—H4122.4 (13)
N6—C5—N5—C1−179.14 (19)C2—C6—N4—N3179.73 (19)
C4—C5—N5—C10.9 (3)C5—C4—C3—C2−1.7 (3)
N6—C5—C4—C3−179.0 (2)C1—C2—C3—C40.6 (3)
N5—C5—C4—C31.0 (3)C6—C2—C3—C4−178.50 (18)
N2—N1—C6—N40.7 (2)C6—N1—N2—N3−0.4 (2)
N2—N1—C6—C2−179.74 (18)C3—C2—C1—N51.2 (3)
C1—C2—C6—N4−173.07 (19)C6—C2—C1—N5−179.71 (18)
C3—C2—C6—N46.0 (3)C5—N5—C1—C2−2.0 (3)
C1—C2—C6—N17.5 (3)N1—N2—N3—N40.0 (2)
C3—C2—C6—N1−173.47 (18)C6—N4—N3—N20.5 (2)
N1—C6—N4—N3−0.7 (2)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1A···O2i0.95 (2)2.55 (2)3.328 (2)138.7 (18)
N1—H1A···O3i0.95 (2)1.84 (3)2.764 (2)163 (2)
N5—H5···O1ii0.91 (2)2.11 (2)2.989 (2)163 (2)
N5—H5···O3ii0.91 (2)2.21 (2)2.908 (2)133.3 (19)
N6—H6A···O1iii0.88 (3)2.31 (3)3.074 (3)145 (2)
N6—H6B···O2iii0.90 (3)2.48 (3)2.908 (2)110 (2)
N6—H6B···N2iv0.90 (3)2.32 (3)3.176 (3)158 (3)
C1—H1···O3ii0.96 (2)2.60 (2)3.124 (2)114.4 (16)
C1—H1···O2i0.96 (2)2.38 (2)3.308 (2)161.5 (18)
C3—H3···N4v0.95 (2)2.55 (2)3.305 (3)136.3 (16)

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: RZ2247).

References

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  • 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]
  • Wittenberger, S. J. & Donner, B. G. (1993). J. Org. Chem.58, 4139–4141.
  • 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]
  • Zou, Y., Hong, S., Park, M., Chun, H. & Lah, M. S. (2007). Chem. Commun.28, 5182–5184. [PubMed]

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