5,5′-(p-Phenyl­ene)di-1H-tetra­zole

Xiang He; Bao-Li An; Ming-Xing Li

doi:10.1107/S1600536807062538

. 2007 Dec 6;64(Pt 1):o40. doi: 10.1107/S1600536807062538

5,5′-(p-Phenylene)di-1H-tetrazole

Xiang He ^a,^*, Bao-Li An ^a, Ming-Xing Li ^a

PMCID: PMC2919293 PMID: 21200915

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 ▶, 2002 ▶); Furmeier & Metzger (2003 ▶); Huang et al. (2005 ▶); Wang et al. (2005 ▶); Xiong et al. (2002 ▶); Ye et al. (2005 ▶).

Experimental

Crystal data

C₈H₆N₈
M _r = 214.21
Monoclinic,
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 ▶) 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
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.23 e Å⁻³

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

Supplementary Material

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

e-64-00o40-sup1.cif^{(12.4KB, cif)}

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

e-64-00o40-Isup2.hkl^{(48.9KB, hkl)}

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3A⋯N4ⁱ	0.86	1.94	2.7805 (15)	167

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Symmetry code: (i) Inline graphic .

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.