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Acta Crystallogr Sect E Struct Rep Online. 2009 June 1; 65(Pt 6): o1391.
Published online 2009 May 23. doi:  10.1107/S1600536809018972
PMCID: PMC2969833

3-(1H-Tetra­zol-5-yl)pyridinium chloride

Abstract

In the cation of the title compound, C6H6N5 +·Cl, the pyridinium and tetra­zole rings are nearly coplanar, making a dihedral angle of 5.05 (12)°. The cations and anions are connected by inter­molecular N—H(...)Cl hydrogen bonds, forming a centrosymmetric [2 + 2] aggregate. The aggregates are stacked along the a axis.

Related literature

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

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Object name is e-65-o1391-scheme1.jpg

Experimental

Crystal data

  • C6H6N5 +·Cl
  • M r = 183.61
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-o1391-efi1.jpg
  • a = 4.2741 (9) Å
  • b = 8.1992 (16) Å
  • c = 23.559 (5) Å
  • β = 94.72 (3)°
  • V = 822.8 (3) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.41 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 = 0.883, T max = 0.921
  • 8164 measured reflections
  • 1862 independent reflections
  • 1431 reflections with I > 2σ(I)
  • R int = 0.041

Refinement

  • R[F 2 > 2σ(F 2)] = 0.040
  • wR(F 2) = 0.104
  • S = 1.03
  • 1862 reflections
  • 109 parameters
  • H-atom parameters constrained
  • Δρmax = 0.22 e Å−3
  • Δρmin = −0.28 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/S1600536809018972/is2410sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809018972/is2410Isup2.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 (Wang et al., 2005; Xiong et al., 2002; Wen, 2008). We report here the crystal structure of the title compound, 3-(1H-tetrazol-5-yl)pyridinium chloride.

In the title compound, the pyridine N atom is protonated (Fig.1). The pyridinium and the tetrazole rings are nearly coplanar and only twisted from each other by a dihedral angle of 5.05 (12) °. 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 aromatic π–π interactions between the benzene rings of the neighbouring cation systems. The Cg···Cgiii distance is 4.274 (2) Å; Cg is the centroide of the C1—C6 benzene ring [symmetry code: (iii) x - 1, y, z]. The molecular packing is further stabilized by intermolecular N—H···Cl hydrogen bonds (Fig. 2 and Table 1).

Experimental

Picolinonitrile (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 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/HCl (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, and 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.
Fig. 2.
The crystal packing of the title compound, viewed approximately along the b axis showing the π–π and N—H···Cl interactions (dotted line) in the title compound. H atoms not involved in hydrogen bonding ...

Crystal data

C6H6N5+·ClF(000) = 376
Mr = 183.61Dx = 1.482 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 1862 reflections
a = 4.2741 (9) Åθ = 3.0–27.3°
b = 8.1992 (16) ŵ = 0.41 mm1
c = 23.559 (5) ÅT = 298 K
β = 94.72 (3)°Block, colorless
V = 822.8 (3) Å30.30 × 0.25 × 0.20 mm
Z = 4

Data collection

Rigaku Mercury2 diffractometer1862 independent reflections
Radiation source: fine-focus sealed tube1431 reflections with I > 2σ(I)
graphiteRint = 0.041
Detector resolution: 13.6612 pixels mm-1θmax = 27.3°, θmin = 3.0°
ω scansh = −5→5
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)k = −10→10
Tmin = 0.883, Tmax = 0.921l = −30→30
8164 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)] = 0.040Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.104H-atom parameters constrained
S = 1.03w = 1/[σ2(Fo2) + (0.0463P)2 + 0.2136P] where P = (Fo2 + 2Fc2)/3
1862 reflections(Δ/σ)max < 0.001
109 parametersΔρmax = 0.22 e Å3
0 restraintsΔρmin = −0.28 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
Cl10.08068 (11)0.24606 (6)0.463087 (19)0.04954 (18)
N10.4537 (4)0.72566 (17)0.43139 (6)0.0410 (4)
H1A0.54370.75210.46410.049*
N20.6191 (4)0.25335 (16)0.35565 (6)0.0389 (4)
H20.73890.26240.38670.047*
N30.5985 (4)0.12105 (19)0.32164 (7)0.0467 (4)
N40.3940 (4)0.1567 (2)0.27942 (7)0.0495 (4)
N50.2793 (4)0.31072 (19)0.28532 (7)0.0446 (4)
C10.5092 (4)0.5771 (2)0.41068 (7)0.0365 (4)
H10.64080.50500.43170.044*
C20.3697 (4)0.53090 (19)0.35769 (6)0.0307 (4)
C30.1717 (4)0.6434 (2)0.32759 (7)0.0373 (4)
H30.07510.61550.29210.045*
C40.1194 (5)0.7958 (2)0.35038 (8)0.0444 (5)
H4−0.01110.87040.33040.053*
C50.2639 (5)0.8356 (2)0.40346 (8)0.0465 (5)
H50.23010.93700.41960.056*
C60.4224 (4)0.3690 (2)0.33340 (7)0.0322 (4)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Cl10.0494 (3)0.0611 (3)0.0360 (3)0.0092 (2)−0.0094 (2)−0.0010 (2)
N10.0493 (9)0.0431 (9)0.0296 (8)0.0010 (7)−0.0028 (7)−0.0053 (6)
N20.0425 (8)0.0389 (8)0.0337 (8)0.0066 (6)−0.0069 (6)−0.0040 (6)
N30.0535 (9)0.0397 (9)0.0459 (9)0.0048 (7)−0.0019 (7)−0.0063 (7)
N40.0576 (10)0.0420 (9)0.0468 (9)0.0019 (7)−0.0084 (8)−0.0098 (7)
N50.0528 (9)0.0392 (8)0.0391 (8)0.0018 (7)−0.0121 (7)−0.0045 (7)
C10.0395 (9)0.0390 (9)0.0298 (8)0.0035 (7)−0.0042 (7)0.0021 (7)
C20.0321 (8)0.0331 (8)0.0265 (8)−0.0003 (7)0.0003 (6)0.0011 (6)
C30.0392 (9)0.0402 (9)0.0311 (8)0.0015 (7)−0.0048 (7)0.0028 (7)
C40.0473 (11)0.0400 (10)0.0450 (11)0.0090 (8)−0.0014 (9)0.0073 (8)
C50.0560 (12)0.0356 (10)0.0482 (11)0.0051 (9)0.0066 (9)−0.0025 (9)
C60.0319 (8)0.0355 (9)0.0286 (8)0.0000 (7)−0.0009 (6)0.0030 (7)

Geometric parameters (Å, °)

N1—C11.340 (2)C1—C21.391 (2)
N1—C51.348 (2)C1—H10.9300
N1—H1A0.8600C2—C31.404 (2)
N2—C61.345 (2)C2—C61.470 (2)
N2—N31.347 (2)C3—C41.385 (3)
N2—H20.8600C3—H30.9300
N3—N41.302 (2)C4—C51.387 (3)
N4—N51.366 (2)C4—H40.9300
N5—C61.331 (2)C5—H50.9300
C1—N1—C5123.19 (15)C2—C3—H3119.8
C1—N1—H1A118.4N4—N3—N2106.29 (14)
C5—N1—H1A118.4C3—C4—C5119.18 (16)
N1—C1—C2119.91 (15)C3—C4—H4120.4
N1—C1—H1120.0C5—C4—H4120.4
C2—C1—H1120.0N3—N4—N5110.72 (14)
C1—C2—C3118.05 (16)C6—N5—N4105.96 (14)
C1—C2—C6121.81 (14)N1—C5—C4119.22 (17)
C3—C2—C6120.13 (14)N1—C5—H5120.4
C6—N2—N3109.14 (14)C4—C5—H5120.4
C6—N2—H2125.4N5—C6—N2107.90 (15)
N3—N2—H2125.4N5—C6—C2125.52 (15)
C4—C3—C2120.44 (16)N2—C6—C2126.58 (14)
C4—C3—H3119.8

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1A···Cl1i0.862.253.0625 (18)157
N2—H2···Cl1ii0.862.233.0790 (18)171

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: IS2410).

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