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Acta Crystallogr Sect E Struct Rep Online. 2009 June 1; 65(Pt 6): o1349.
Published online 2009 May 20. doi:  10.1107/S1600536809018200
PMCID: PMC2969801

4-(2H-Tetra­zol-5-yl)pyridinium perchlorate

Abstract

In the cation of the title compound, C6H6N5 +·ClO4 , the pyridinium and tetra­zole rings form a dihedral angle of 23.6 (1)°. In the crystal structure, weak inter­molecular N—H(...)O and N—H(...)N hydrogen bonds link cations and anions into chains extending along the b axis.

Related literature

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

An external file that holds a picture, illustration, etc.
Object name is e-65-o1349-scheme1.jpg

Experimental

Crystal data

  • C6H6N5 +·ClO4
  • M r = 247.61
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-o1349-efi1.jpg
  • a = 5.2033 (10) Å
  • b = 14.764 (3) Å
  • c = 12.244 (2) Å
  • β = 101.78 (3)°
  • V = 920.8 (3) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.43 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 = 0.872, T max = 1.000 (expected range = 0.801–0.919)
  • 9546 measured reflections
  • 2108 independent reflections
  • 1849 reflections with I > 2σ(I)
  • R int = 0.036

Refinement

  • R[F 2 > 2σ(F 2)] = 0.035
  • wR(F 2) = 0.093
  • S = 1.09
  • 2108 reflections
  • 146 parameters
  • H-atom parameters constrained
  • Δρmax = 0.29 e Å−3
  • Δρmin = −0.37 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/S1600536809018200/cv2545sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809018200/cv2545Isup2.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 their attention 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 (Wang et al. 2005; Xiong et al. 2002; Wen, 2008). We report here the crystal structure of the title compound, 4-(2H-tetrazol-5-yl)pyridinium perchlorate).

In the title compound (Fig.1), the pyridine N atom is protonated. The pyridine ring makes a dihedral angle of 23.62 (1)° with the tetrazole ring. The geometric parameters of the tetrazole rings are comparable to those in related molecules (Wang et al. 2005; Dai & Fu, 2008).

The crystal packing is stabilized by N—H···O and N—H···N hydrogen bonds (Table 1) with the formation of zig-zag chains parallel to b axis.

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) 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/HClO4 (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 (aromatic) and N–H = 0.86 Å with Uiso(H) =1.2Ueq(C or N).

Figures

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

Crystal data

C6H6N5+·ClO4F(000) = 504
Mr = 247.61Dx = 1.786 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 2108 reflections
a = 5.2033 (10) Åθ = 3.2–27.5°
b = 14.764 (3) ŵ = 0.43 mm1
c = 12.244 (2) ÅT = 298 K
β = 101.78 (3)°Block, colourless
V = 920.8 (3) Å30.30 × 0.25 × 0.20 mm
Z = 4

Data collection

Rigaku Mercury2 diffractometer2108 independent reflections
Radiation source: fine-focus sealed tube1849 reflections with I > 2σ(I)
graphiteRint = 0.036
Detector resolution: 13.6612 pixels mm-1θmax = 27.5°, θmin = 3.2°
CCD profile fitting scansh = −6→6
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)k = −19→19
Tmin = 0.872, Tmax = 1.000l = −15→15
9546 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)] = 0.035H-atom parameters constrained
wR(F2) = 0.093w = 1/[σ2(Fo2) + (0.0391P)2 + 0.4636P] where P = (Fo2 + 2Fc2)/3
S = 1.09(Δ/σ)max < 0.001
2108 reflectionsΔρmax = 0.29 e Å3
146 parametersΔρmin = −0.37 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: 0.032 (3)

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
Cl10.54774 (8)0.68556 (3)0.60933 (3)0.02861 (15)
O40.6154 (3)0.76134 (10)0.54624 (12)0.0425 (4)
O30.2704 (3)0.68626 (10)0.60633 (13)0.0433 (4)
O20.6150 (3)0.60331 (10)0.55912 (15)0.0524 (4)
N10.3679 (3)0.59831 (10)0.88383 (13)0.0307 (3)
N50.0708 (3)0.33991 (11)0.61681 (12)0.0317 (3)
H5A−0.01010.30290.56730.038*
N40.7318 (3)0.51759 (10)0.89177 (13)0.0325 (4)
C30.3301 (3)0.45759 (11)0.77061 (13)0.0247 (3)
C60.4761 (3)0.52315 (11)0.85006 (13)0.0246 (3)
N20.5614 (3)0.64262 (10)0.94760 (13)0.0327 (4)
C50.2877 (4)0.31159 (12)0.68590 (16)0.0337 (4)
H50.34710.25260.68100.040*
N30.7722 (3)0.59329 (10)0.95023 (13)0.0325 (4)
H3A0.92460.60900.98710.039*
O10.6915 (3)0.69193 (12)0.72169 (12)0.0516 (4)
C20.0996 (3)0.48426 (12)0.69840 (15)0.0298 (4)
H20.03270.54230.70260.036*
C40.4234 (4)0.37000 (12)0.76447 (15)0.0308 (4)
H40.57560.35110.81290.037*
C1−0.0268 (4)0.42336 (13)0.62097 (15)0.0334 (4)
H1−0.17990.44010.57160.040*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Cl10.0264 (2)0.0283 (2)0.0283 (2)−0.00122 (15)−0.00104 (16)0.00377 (16)
O40.0439 (8)0.0389 (8)0.0435 (8)−0.0015 (6)0.0060 (6)0.0151 (6)
O30.0268 (7)0.0536 (9)0.0482 (8)−0.0018 (6)0.0044 (6)−0.0002 (7)
O20.0510 (9)0.0366 (8)0.0687 (11)0.0080 (7)0.0098 (8)−0.0074 (7)
N10.0302 (8)0.0249 (8)0.0349 (8)−0.0011 (6)0.0013 (6)−0.0052 (6)
N50.0349 (8)0.0290 (8)0.0287 (8)−0.0066 (6)0.0006 (6)−0.0077 (6)
N40.0284 (8)0.0285 (8)0.0371 (8)0.0002 (6)−0.0016 (6)−0.0049 (6)
C30.0260 (8)0.0227 (8)0.0247 (8)−0.0023 (6)0.0036 (6)−0.0002 (6)
C60.0262 (8)0.0215 (8)0.0244 (8)0.0000 (6)0.0012 (6)0.0007 (6)
N20.0346 (8)0.0266 (8)0.0344 (8)−0.0041 (6)0.0014 (6)−0.0049 (6)
C50.0423 (11)0.0224 (9)0.0348 (10)0.0007 (7)0.0037 (8)−0.0026 (7)
N30.0289 (8)0.0293 (8)0.0348 (8)−0.0038 (6)−0.0038 (6)−0.0047 (6)
O10.0471 (9)0.0699 (11)0.0306 (8)−0.0147 (7)−0.0092 (6)0.0103 (7)
C20.0291 (9)0.0249 (9)0.0328 (9)0.0015 (7)0.0003 (7)−0.0014 (7)
C40.0331 (9)0.0247 (9)0.0304 (9)0.0024 (7)−0.0030 (7)−0.0009 (7)
C10.0294 (9)0.0345 (10)0.0325 (9)−0.0008 (7)−0.0027 (7)−0.0011 (8)

Geometric parameters (Å, °)

Cl1—O11.4285 (15)C3—C41.389 (2)
Cl1—O21.4363 (15)C3—C21.394 (2)
Cl1—O31.4363 (15)C3—C61.469 (2)
Cl1—O41.4433 (14)N2—N31.312 (2)
N1—N21.315 (2)C5—C41.375 (2)
N1—C61.347 (2)C5—H50.9300
N5—C51.332 (2)N3—H3A0.8600
N5—C11.338 (2)C2—C11.373 (2)
N5—H5A0.8600C2—H20.9300
N4—N31.321 (2)C4—H40.9300
N4—C61.327 (2)C1—H10.9300
O1—Cl1—O2110.02 (11)N3—N2—N1105.86 (15)
O1—Cl1—O3110.48 (10)N5—C5—C4119.66 (17)
O2—Cl1—O3109.06 (9)N5—C5—H5120.2
O1—Cl1—O4109.12 (9)C4—C5—H5120.2
O2—Cl1—O4108.60 (10)N2—N3—N4114.64 (14)
O3—Cl1—O4109.53 (9)N2—N3—H3A122.7
N2—N1—C6105.96 (15)N4—N3—H3A122.7
C5—N5—C1122.96 (15)C1—C2—C3118.82 (16)
C5—N5—H5A118.5C1—C2—H2120.6
C1—N5—H5A118.5C3—C2—H2120.6
N3—N4—C6101.09 (14)C5—C4—C3119.14 (16)
C4—C3—C2119.59 (15)C5—C4—H4120.4
C4—C3—C6120.69 (15)C3—C4—H4120.4
C2—C3—C6119.70 (15)N5—C1—C2119.82 (16)
N4—C6—N1112.45 (15)N5—C1—H1120.1
N4—C6—C3123.79 (15)C2—C1—H1120.1
N1—C6—C3123.66 (15)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N5—H5A···O3i0.862.282.964 (2)136
N5—H5A···N2ii0.862.383.059 (2)136
N3—H3A···O4iii0.862.212.884 (2)135

Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x+1/2, y−1/2, −z+3/2; (iii) x+1/2, −y+3/2, z+1/2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: CV2545).

References

  • Dai, W. & Fu, D.-W. (2008). Acta Cryst. E64, o1444. [PMC free article] [PubMed]
  • 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]

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography