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Acta Crystallogr Sect E Struct Rep Online. 2008 January 1; 64(Pt 1): o40.
Published online 2007 December 6. doi:  10.1107/S1600536807062538
PMCID: PMC2919293

5,5′-(p-Phenyl­ene)di-1H-tetra­zole

Abstract

Crystals of the title organic compound, C8H6N8, were generated in situ through the [2 + 3]-cyclo­addition reaction involving the precursor 1,4-dicyano­benzene and azide in water with Zn2+ as Lewis acid. The asymmetric unit consists of one half-mol­ecule, and a twofold axis of symmetry passes through the centre of the benzene ring. There is an inter­molecular N—H(...)N hydrogen bond. The mol­ecules are assembled into a three-dimensional supra­molecular framework by π–π stacking inter­actions, with a perpendicular distance of 3.256 Å [centroid–centroid = 3.9731 (8) Å] between two tetra­zole ring planes, and 3.382 Å between the benz­ene ring and tetra­zole ring planes [centroid–centroid = 3.5010 (9) Å].

Related literature

For related literature, see: Demko & Sharpless (2001 [triangle], 2002 [triangle]); Furmeier & Metzger (2003 [triangle]); Huang et al. (2005 [triangle]); Wang et al. (2005 [triangle]); Xiong et al. (2002 [triangle]); Ye et al. (2005 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-64-00o40-scheme1.jpg

Experimental

Crystal data

  • C8H6N8
  • M r = 214.21
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-00o40-efi1.jpg
  • a = 4.5396 (4) Å
  • b = 9.8219 (10) Å
  • c = 9.7525 (10) Å
  • β = 92.910 (5)°
  • V = 434.28 (7) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 0.12 mm−1
  • T = 293 (2) K
  • 0.70 × 0.12 × 0.10 mm

Data collection

  • Siemens SMART CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Siemens, 1996 [triangle]) T min = 0.701, T max = 1.000 (expected range = 0.693–0.988)
  • 3228 measured reflections
  • 985 independent reflections
  • 830 reflections with I > 2σ(I)
  • R int = 0.037

Refinement

  • R[F 2 > 2σ(F 2)] = 0.036
  • wR(F 2) = 0.106
  • S = 1.07
  • 985 reflections
  • 73 parameters
  • H-atom parameters constrained
  • Δρmax = 0.26 e Å−3
  • Δρmin = −0.23 e Å−3

Data collection: SMART (Siemens, 1996 [triangle]); cell refinement: SAINT (Siemens, 1996 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2000 [triangle]); software used to prepare material for publication: SHELXTL.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536807062538/at2504sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536807062538/at2504Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

This work was supported by the Development Foundation of Shanghai Municipal Education Commission, and the Science Foundation for Excellent Youth Scholars of Higher Education of Shanghai.

supplementary crystallographic information

Comment

Owing to the efforts of Sharpless and Demko in the past years, the preparation of 5-substituted tetrazolate ligands has now become a safe and convenient procedure (Demko et al., 2001). Recently, Metzger and Furmeier reported that 5-substituted tetrazolates can also be synthesized from nitriles in toluene (Furmeier et al., 2003), and Xiong et al. reported several coordination polymers obtained from the reaction of the tetrazoles generated in situ with a variety of 5-substituted groups under hydrothermal conditions (Xiong et al., 2002). However, the coordination polymers containing the ligands synthesized in situ from the precursor ligands containing two-cyano groups have rarely been reported (Huang et al., 2005; Wang et al., 2005). Herein we report the title compound (I).

The title compound is composed of 5,5'-(1,4-phenylene)bis(1H-tetrazole). As shown in Fig. 1, the asymmetric unit consists of one-half molecule, a twofold axis of symmetry passes through the centre of phenylene. There is a hydrogen bond; N3···N4 (x, -y + 3/2, z + 1/2) of 2.7805 (15) Å. The hydrogen bond and aromatic π-π -stacking interactions assemble the organic molecules into a three-dimensional supramolecular framework (Fig.2). Within the framework, the tetrazolyl ring (N1—N4/C9) at (x, y, z) is parallel to the tetrazolyl ring at (-x,1 - y,1 - z) and the perpendicular distance between the two ring planes is 3.256 Å, with the distance between ring centroids is 3.9731 (8) Å. The phenylene ring (C6—C8/C6i—C8i) [(i) -x - 1,-y + 2,-z + 1] is almost parallel to the tetrazolyl ring at (-x,-y,1 - z) with a dihedral angle of 2.69°, and the perpendicular distance of phenylene ring on tetrazolyl ring planes is 3.382 Å, with the distance between ring centroids is 3.5010 (9) Å. The supramolecular structure is stabilized by aromatic π-π-stacking interactions.

Experimental

A mixture of ZnCl2 (1.5 mmol), 1,4-dicyanobenzene (1 mmol) and azide (3 mmol) in 15 ml H2O was heated at 160oC for three days in a sealed 25 ml Teflon-Lined stainless steel vessel under autogenous pressure. After the reaction mixture was slowly cooled down to room temperature, colorless prismlike crystals were produced, which were collected by filtration and washed with distilled water and dried in air.

Refinement

H atoms were placed in idealized positions, with with C—H distances of 0.93 Å, N—H distances of 0.86 Å, and allowed to ride on their respective parent C atoms with the constraint Uiso(H) = 1.2Ueq(C).

Figures

Fig. 1.
A perspective view of the locally expanded unit for (I). Displacement ellipsoids are drawn at the 30% probability level [symmetry codes: (i) -x-1,-y+2,-z+1].
Fig. 2.
Crystal packing diagram of compound (I).

Crystal data

C8H6N8F(000) = 220
Mr = 214.21Dx = 1.638 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 1058 reflections
a = 4.5396 (4) Åθ = 4.2–27.5°
b = 9.8219 (10) ŵ = 0.12 mm1
c = 9.7525 (10) ÅT = 293 K
β = 92.910 (5)°Prism, colourless
V = 434.28 (7) Å30.70 × 0.12 × 0.10 mm
Z = 2

Data collection

Siemens SMART CCD diffractometer985 independent reflections
Radiation source: fine-focus sealed tube830 reflections with I > 2σ(I)
graphiteRint = 0.037
Detector resolution: ω pixels mm-1θmax = 27.5°, θmin = 4.2°
dtprofit.ref scansh = −5→5
Absorption correction: multi-scan (SADABS; Siemens, 1996)k = −12→10
Tmin = 0.701, Tmax = 1.000l = −12→12
3228 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)] = 0.036Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.106H-atom parameters constrained
S = 1.07w = 1/[σ2(Fo2) + (0.0565P)2 + 0.0841P] where P = (Fo2 + 2Fc2)/3
985 reflections(Δ/σ)max < 0.001
73 parametersΔρmax = 0.26 e Å3
0 restraintsΔρmin = −0.23 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
N10.2260 (3)0.63240 (12)0.42296 (11)0.0191 (3)
N20.2387 (3)0.62431 (12)0.55599 (11)0.0188 (3)
C9−0.0803 (3)0.78246 (13)0.49215 (12)0.0138 (3)
C6−0.2968 (3)0.89304 (13)0.49702 (12)0.0142 (3)
C7−0.5995 (3)1.04419 (14)0.62493 (13)0.0167 (3)
H7A−0.66621.07380.70850.020*
C8−0.3988 (3)0.93858 (14)0.62200 (13)0.0167 (3)
H8A−0.33120.89750.70360.020*
N40.0286 (3)0.73052 (11)0.37995 (11)0.0166 (3)
N30.0463 (3)0.71737 (11)0.60025 (11)0.0159 (3)
H3A0.01080.73240.68470.019*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
N10.0222 (7)0.0192 (6)0.0159 (6)0.0010 (5)0.0004 (5)−0.0008 (4)
N20.0221 (7)0.0176 (6)0.0167 (6)0.0014 (5)0.0015 (5)−0.0015 (4)
C90.0145 (7)0.0150 (7)0.0118 (6)−0.0047 (5)−0.0007 (5)0.0003 (4)
C60.0141 (6)0.0150 (6)0.0133 (6)−0.0033 (5)−0.0009 (5)0.0007 (5)
C70.0199 (7)0.0198 (7)0.0105 (6)−0.0001 (6)0.0014 (5)−0.0007 (5)
C80.0190 (7)0.0197 (7)0.0113 (6)−0.0002 (5)−0.0010 (5)0.0027 (5)
N40.0190 (6)0.0179 (6)0.0129 (5)0.0002 (5)0.0000 (4)−0.0006 (4)
N30.0194 (6)0.0172 (6)0.0112 (5)0.0008 (5)0.0012 (4)−0.0002 (4)

Geometric parameters (Å, °)

N1—N21.2982 (16)C6—C81.3991 (18)
N1—N41.3674 (16)C7—C81.3819 (19)
N2—N31.3499 (16)C7—C6i1.3997 (17)
C9—N41.3256 (17)C7—H7A0.9300
C9—N31.3376 (16)C8—H8A0.9300
C9—C61.4672 (18)N3—H3A0.8600
C6—C7i1.3997 (17)
N2—N1—N4110.17 (11)C8—C7—H7A119.8
N1—N2—N3106.36 (10)C6i—C7—H7A119.8
N4—C9—N3107.65 (12)C7—C8—C6120.38 (12)
N4—C9—C6126.17 (11)C7—C8—H8A119.8
N3—C9—C6126.17 (12)C6—C8—H8A119.8
C7i—C6—C8119.18 (13)C9—N4—N1106.51 (10)
C7i—C6—C9119.70 (12)C9—N3—N2109.31 (11)
C8—C6—C9121.11 (12)C9—N3—H3A125.3
C8—C7—C6i120.44 (12)N2—N3—H3A125.3
N4—N1—N2—N30.39 (14)C9—C6—C8—C7179.05 (12)
N4—C9—C6—C7i−1.7 (2)N3—C9—N4—N1−0.25 (15)
N3—C9—C6—C7i177.09 (13)C6—C9—N4—N1178.76 (12)
N4—C9—C6—C8179.24 (13)N2—N1—N4—C9−0.09 (15)
N3—C9—C6—C8−1.9 (2)N4—C9—N3—N20.50 (15)
C6i—C7—C8—C60.0 (2)C6—C9—N3—N2−178.51 (12)
C7i—C6—C8—C70.0 (2)N1—N2—N3—C9−0.55 (15)

Symmetry codes: (i) −x−1, −y+2, −z+1.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N3—H3A···N4ii0.861.942.7805 (15)167

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: AT2504).

References

  • Demko, Z. P. & Sharpless, K. B. (2001). Org. Lett.3, 4091–4094. [PubMed]
  • Demko, Z. P. & Sharpless, K. B. (2002). Angew. Chem. Int. Ed.41, 2110–2113. [PubMed]
  • Furmeier, S. & Metzger, J. Q. (2003). Eur. J. Org. Chem. pp. 885–893.
  • Huang, X.-F., Song, Y.-M., Wu, Q., Ye, Q., Chen, X.-B., Xiong, R.-G. & You, X.-Z. (2005). Inorg. Chem. Commun.8, 58–60.
  • Sheldrick, G. M. (1997). SHELXS97 and SHELXL97 University of Göttingen, Germany.
  • Sheldrick, G. M. (2000). SHELXTL Version 6.1. Bruker AXS Inc., Madison, Wisconsin, USA.
  • Siemens (1996). SMART, SAINT and SADABS Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.
  • Wang, X.-S., Huang, X.-F. & Xiong, R.-G. (2005). Chin. J. Inorg. Chem.21, 1020–1024.
  • 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]
  • Ye, Q., Tang, Y.-Z., Wang, X.-S. & Xiong, R.-G. (2005). Dalton Trans. pp. 1570–1573. [PubMed]

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