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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 67| Part 1| January 2011| Page o43
https://doi.org/10.1107/S1600536810050257

5-(Pyridinium-4-yl)-1H-1,2,3,4-tetra­zol-1-ide

Qian Xua* and Jie Xua

aOrdered Matter Science Research Center, College of Chemistry and Chemical Engineering, Southeast University, Nanjing 210096, People's Republic of China
*Correspondence e-mail: xqchem@yahoo.com.cn

(Received 17 November 2010; accepted 1 December 2010; online 8 December 2010)

In the title zwitterionic mol­ecule, C6H5N5, the tetra­zole and pyridine rings are nearly coplanar, making a dihedral angle of 2.08 (1)°. In the crystal, mol­ecules are connected by classical N—H⋯N and weak C—H⋯N hydrogen bonds.

Related literature

For applications of tetra­zole derivatives, see: Zhao et al. (2008[Zhao, H., Qu, Z.-R., Ye, H.-Y. & Xiong, R.-G. (2008). Chem. Soc. Rev. 37, 84-100.]); Fu et al. (2008[Fu, D.-W., Zhang, W. & Xiong, R.-G. (2008). Cryst. Growth Des. 8, 3461-3464.], 2009[Fu, D.-W., Ge, J.-Z., Dai, J., Ye, H.-Y. & Qu, Z.-R. (2009). Inorg. Chem. Commun. 12, 994-997.]). For the crystal structures and properties of related compounds, see: Fu et al. (2007[Fu, D.-W., Song, Y.-M., Wang, G.-X., Ye, Q., Xiong, R.-G., Akutagawa, T., Nakamura, T., Chan, P. W. H. & Huang, S.-P.-D. (2007). J. Am. Chem. Soc. 129, 5346-5347.], 2009[Fu, D.-W., Ge, J.-Z., Dai, J., Ye, H.-Y. & Qu, Z.-R. (2009). Inorg. Chem. Commun. 12, 994-997.]); Fu & Xiong (2008[Fu, D.-W. & Xiong, R.-G. (2008). Dalton Trans. pp. 3946-3948.]).

[Scheme 1]

Experimental

Crystal data

  • C6H5N5

  • Mr = 147.15

  • Monoclinic, C c

  • a = 7.0508 (14) Å

  • b = 7.4007 (15) Å

  • c = 11.926 (2) Å

  • β = 96.56 (3)°

  • V = 618.2 (2) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 0.11 mm−1

  • T = 298 K

  • 0.30 × 0.20 × 0.15 mm
Data collection

  • Rigaku Mercury2 diffractometer

  • 3122 measured reflections

  • 719 independent reflections

  • 633 reflections with I > 2σ(I)

  • Rint = 0.039
Refinement

  • R[F2 > 2σ(F2)] = 0.040

  • wR(F2) = 0.096

  • S = 1.13

  • 719 reflections

  • 100 parameters

  • 2 restraints

  • H-atom parameters constrained

  • Δρmax = 0.23 e Å−3

  • Δρmin = −0.21 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A D⋯A D—H⋯A
N1—H1A⋯N2i 0.86 1.89 2.745 (4) 176
N1—H1A⋯N3i 0.86 2.52 3.306 (4) 152
C1—H1⋯N5ii 0.93 2.46 3.308 (4) 152
C5—H5⋯N4iii 0.93 2.38 3.168 (4) 142
Symmetry codes: (i) [x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]; (ii) x, y+1, z; (iii) [x+{\script{1\over 2}}, -y-{\script{1\over 2}}, z+{\script{1\over 2}}].

Data collection: CrystalClear (Rigaku, 2005[Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan.]); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536810050257/xu5093sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810050257/xu5093Isup2.hkl

checkCIF report


Comment top

Tetrazole compounds attracted more attention as phase transition dielectric materials for its application in micro-electronics, memory storage. With the purpose of obtaining phase transition crystals of tetrazole compound, a series of new materials have been elaborated with this organic molecule (Zhao et al., 2008; Fu et al., 2008; Fu et al., 2007; Fu & Xiong 2008). We report here the crystal structure of the title compound, 5-(pyridinium-4-yl)tetrazol-1-ide.

The dielectric constant of title compound as a function of temperature indicates that the permittivity is basically temperature-independent, suggesting that this compound should be not a real ferroelectrics or there may be no distinct phase transition occurred within the measured temperature range. Similarly, below the melting point (413K) of the compound, the dielectric constant as a function of temperature also goes smoothly, and there is no dielectric anomaly observed (dielectric constant equaling to 6.1 to 7.9).

In the title compound (Fig.1), the pyridine N atom is protonated, thus indicating a positive charge in the pyridine N atom. And the tetrazole ring was showing a negative charge to make the charge balance. The tetrazole and pyridine rings are twisted from each other by a dihedral angle of 2.08 (1)°. The geometric parameters of the tetrazole rings are comparable to those in related molecules (Fu et al., 2009).

In the crystal structure the molecules are connected by classic N—H···N and weak C—H···N hydrogen bonds (Table 1).

Related literature top

For applications of tetrazole derivatives, see: Zhao et al. (2008); Fu et al. (2008, 2009). For the crystal structures and properties of related compounds, see: Fu et al. (2007, 2009); Fu & Xiong (2008).

Experimental top

5-(Pyridinium-4-yl)tetrazol-1-ide was obtained commercially, and the single crystals were obtained from an ethanol solution.

Refinement top

H atoms attached to N atoms were located in a difference Fourier map, and refined in riding mode with N–H = 0.86 Å and Uiso(H) = 1.2Ueq(N). Other H atoms were fixed geometrically and treated as riding with C–H = 0.93 Å and Uiso(H) = 1.2Ueq(C). As no significant anomalous scattering, Friedel pairs were merged.

Structure description top

Tetrazole compounds attracted more attention as phase transition dielectric materials for its application in micro-electronics, memory storage. With the purpose of obtaining phase transition crystals of tetrazole compound, a series of new materials have been elaborated with this organic molecule (Zhao et al., 2008; Fu et al., 2008; Fu et al., 2007; Fu & Xiong 2008). We report here the crystal structure of the title compound, 5-(pyridinium-4-yl)tetrazol-1-ide.

The dielectric constant of title compound as a function of temperature indicates that the permittivity is basically temperature-independent, suggesting that this compound should be not a real ferroelectrics or there may be no distinct phase transition occurred within the measured temperature range. Similarly, below the melting point (413K) of the compound, the dielectric constant as a function of temperature also goes smoothly, and there is no dielectric anomaly observed (dielectric constant equaling to 6.1 to 7.9).

In the title compound (Fig.1), the pyridine N atom is protonated, thus indicating a positive charge in the pyridine N atom. And the tetrazole ring was showing a negative charge to make the charge balance. The tetrazole and pyridine rings are twisted from each other by a dihedral angle of 2.08 (1)°. The geometric parameters of the tetrazole rings are comparable to those in related molecules (Fu et al., 2009).

In the crystal structure the molecules are connected by classic N—H···N and weak C—H···N hydrogen bonds (Table 1).

For applications of tetrazole derivatives, see: Zhao et al. (2008); Fu et al. (2008, 2009). For the crystal structures and properties of related compounds, see: Fu et al. (2007, 2009); Fu & Xiong (2008).

Computing details top

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

Figures top
[Figure 1] Fig. 1. A view of the title compound with the atomic numbering scheme. Displacement ellipsoids were drawn at the 30% probability level.
5-(Pyridinium-4-yl)-1H-1,2,3,4-tetrazol-1-ide top
Crystal data top
C6H5N5F(000) = 304
Mr = 147.15Dx = 1.581 Mg m−3
Monoclinic, CcMo Kα radiation, λ = 0.71073 Å
Hall symbol: C -2ycCell parameters from 1425 reflections
a = 7.0508 (14) Åθ = 3.4–24.5°
b = 7.4007 (15) ŵ = 0.11 mm−1
c = 11.926 (2) ÅT = 298 K
β = 96.56 (3)°Block, colorless
V = 618.2 (2) Å30.30 × 0.20 × 0.15 mm
Z = 4
Data collection top
Rigaku Mercury2
diffractometer		633 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.039
Graphite monochromatorθmax = 27.5°, θmin = 3.4°
Detector resolution: 13.6612 pixels mm-1h = −9→9
CCD profile fitting scansk = −9→9
3122 measured reflectionsl = −15→15
719 independent reflections
Refinement top
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) = 0.096H-atom parameters constrained
S = 1.13 w = 1/[σ2(Fo2) + (0.056P)2]
where P = (Fo2 + 2Fc2)/3
719 reflections(Δ/σ)max < 0.001
100 parametersΔρmax = 0.23 e Å−3
2 restraintsΔρmin = −0.21 e Å−3
Crystal data top
C6H5N5V = 618.2 (2) Å3
Mr = 147.15Z = 4
Monoclinic, CcMo Kα radiation
a = 7.0508 (14) ŵ = 0.11 mm−1
b = 7.4007 (15) ÅT = 298 K
c = 11.926 (2) Å0.30 × 0.20 × 0.15 mm
β = 96.56 (3)°
Data collection top
Rigaku Mercury2
diffractometer		633 reflections with I > 2σ(I)
3122 measured reflectionsRint = 0.039
719 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0402 restraints
wR(F2) = 0.096H-atom parameters constrained
S = 1.13Δρmax = 0.23 e Å−3
719 reflectionsΔρmin = −0.21 e Å−3
100 parameters
Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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) top
xyzUiso*/Ueq
N11.0961 (4)0.3035 (4)0.4442 (2)0.0382 (6)
H1A1.14620.37910.49370.046*
N20.7525 (4)−0.0341 (4)0.1099 (2)0.0375 (6)
N30.7094 (4)−0.1968 (3)0.0653 (2)0.0443 (7)
N40.7884 (4)−0.3224 (3)0.1321 (2)0.0444 (8)
N50.8864 (3)−0.2457 (4)0.2218 (2)0.0395 (7)
C10.9963 (5)0.3659 (4)0.3504 (3)0.0397 (9)
H10.98050.48960.33940.048*
C20.9185 (4)0.2487 (4)0.2718 (3)0.0368 (7)
H20.84960.29200.20620.044*
C30.9406 (4)0.0634 (4)0.2879 (2)0.0290 (6)
C41.0442 (4)0.0050 (4)0.3861 (2)0.0372 (8)
H41.0622−0.11790.39960.045*
C51.1202 (4)0.1280 (4)0.4632 (3)0.0391 (7)
H51.18960.08880.52980.047*
C60.8605 (4)−0.0704 (4)0.2067 (2)0.0305 (7)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0486 (14)0.0342 (16)0.0299 (14)−0.0035 (13)−0.0037 (10)−0.0059 (13)
N20.0465 (15)0.0288 (12)0.0353 (13)0.0003 (11)−0.0040 (10)0.0010 (11)
N30.0595 (17)0.0348 (13)0.0359 (13)−0.0060 (15)−0.0060 (11)−0.0082 (14)
N40.062 (2)0.0293 (14)0.0404 (19)−0.0004 (13)−0.0010 (15)−0.0045 (12)
N50.0533 (16)0.0251 (13)0.0377 (16)0.0014 (11)−0.0051 (13)−0.0026 (11)
C10.0455 (17)0.029 (2)0.0431 (16)0.0041 (15)0.0005 (13)0.0020 (15)
C20.0422 (17)0.0311 (16)0.0346 (16)0.0031 (13)−0.0059 (12)0.0052 (13)
C30.0355 (14)0.0240 (15)0.0264 (13)0.0001 (12)−0.0007 (11)−0.0009 (11)
C40.0514 (19)0.0257 (18)0.0319 (15)0.0008 (12)−0.0060 (12)−0.0004 (13)
C50.0512 (18)0.0331 (16)0.0304 (14)0.0035 (14)−0.0069 (13)−0.0014 (13)
C60.0369 (16)0.0263 (15)0.0272 (14)0.0002 (12)−0.0016 (11)0.0014 (13)
Geometric parameters (Å, º) top
N1—C51.325 (4)C1—H10.9300
N1—C11.334 (5)C2—C31.391 (4)
N1—H1A0.8600C2—H20.9300
N2—C61.335 (4)C3—C41.377 (4)
N2—N31.337 (4)C3—C61.453 (4)
N3—N41.306 (4)C4—C51.359 (4)
N4—N51.333 (4)C4—H40.9300
N5—C61.320 (4)C5—H50.9300
C1—C21.348 (5)
C5—N1—C1121.8 (3)C4—C3—C2117.8 (3)
C5—N1—H1A119.1C4—C3—C6118.8 (2)
C1—N1—H1A119.1C2—C3—C6123.4 (2)
C6—N2—N3104.1 (3)C5—C4—C3119.6 (3)
N4—N3—N2109.6 (3)C5—C4—H4120.2
N3—N4—N5109.4 (2)C3—C4—H4120.2
C6—N5—N4104.9 (2)N1—C5—C4120.5 (3)
N1—C1—C2119.6 (3)N1—C5—H5119.7
N1—C1—H1120.2C4—C5—H5119.7
C2—C1—H1120.2N5—C6—N2111.8 (3)
C1—C2—C3120.5 (3)N5—C6—C3122.8 (2)
C1—C2—H2119.7N2—C6—C3125.4 (3)
C3—C2—H2119.7
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···N2i0.861.892.745 (4)176
N1—H1A···N3i0.862.523.306 (4)152
C1—H1···N5ii0.932.463.308 (4)152
C5—H5···N4iii0.932.383.168 (4)142
Symmetry codes: (i) x+1/2, −y+1/2, z+1/2; (ii) x, y+1, z; (iii) x+1/2, −y−1/2, z+1/2.

Experimental details

Crystal data
Chemical formulaC6H5N5
Mr147.15
Crystal system, space groupMonoclinic, Cc
Temperature (K)298
a, b, c (Å)7.0508 (14), 7.4007 (15), 11.926 (2)
β (°) 96.56 (3)
V (Å3)618.2 (2)
Z4
Radiation typeMo Kα
µ (mm−1)0.11
Crystal size (mm)0.30 × 0.20 × 0.15
Data collection
DiffractometerRigaku Mercury2
Absorption correction–
No. of measured, independent and
observed [I > 2σ(I)] reflections		3122, 719, 633
Rint0.039
(sin θ/λ)max (Å−1)0.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.040, 0.096, 1.13
No. of reflections719
No. of parameters100
No. of restraints2
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å−3)0.23, −0.21

Computer programs: CrystalClear (Rigaku, 2005), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···N2i0.861.892.745 (4)176
N1—H1A···N3i0.862.523.306 (4)152
C1—H1···N5ii0.932.463.308 (4)152
C5—H5···N4iii0.932.383.168 (4)142
Symmetry codes: (i) x+1/2, −y+1/2, z+1/2; (ii) x, y+1, z; (iii) x+1/2, −y−1/2, z+1/2.
 

Acknowledgements

This work was supported by a start-up grant from Southeast University, China.

References

First citationFu, D.-W., Ge, J.-Z., Dai, J., Ye, H.-Y. & Qu, Z.-R. (2009). Inorg. Chem. Commun. 12, 994–997.  Web of Science CSD CrossRef CAS Google Scholar
 First citationFu, D.-W., Song, Y.-M., Wang, G.-X., Ye, Q., Xiong, R.-G., Akutagawa, T., Nakamura, T., Chan, P. W. H. & Huang, S.-P.-D. (2007). J. Am. Chem. Soc. 129, 5346–5347.  Web of Science CSD CrossRef PubMed CAS Google Scholar
 First citationFu, D.-W. & Xiong, R.-G. (2008). Dalton Trans. pp. 3946–3948.  Web of Science CSD CrossRef Google Scholar
 First citationFu, D.-W., Zhang, W. & Xiong, R.-G. (2008). Cryst. Growth Des. 8, 3461–3464.  Web of Science CSD CrossRef CAS Google Scholar
 First citationRigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan.  Google Scholar
 First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
 First citationZhao, H., Qu, Z.-R., Ye, H.-Y. & Xiong, R.-G. (2008). Chem. Soc. Rev. 37, 84–100.  Web of Science CrossRef PubMed Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 67| Part 1| January 2011| Page o43
https://doi.org/10.1107/S1600536810050257
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