Benzene-1,3,5-tricarb­oxy­lic acid–5-(pyridin-1-ium-3-yl)-5H-1,2,3,4-tetra­zol-5-ide (1/1)

Gao-Xiang Meng; Hao Ding; Ya-Min Feng; Jian-Hui Zhu; He-Lin Yang

doi:10.1107/S1600536811021490

. 2011 Jun 11;67(Pt 7):o1620. doi: 10.1107/S1600536811021490

Benzene-1,3,5-tricarboxylic acid–5-(pyridin-1-ium-3-yl)-5H-1,2,3,4-tetrazol-5-ide (1/1)

Gao-Xiang Meng ^a, Hao Ding ^a, Ya-Min Feng ^a, Jian-Hui Zhu ^a, He-Lin Yang ^a,^*

PMCID: PMC3151784 PMID: 21837026

Abstract

The asymmetric unit of the title compound, C₆H₅N₅·C₉H₆O₆, comprises a full molecule each of neutral trimesic acid (tma) and zwitterionic 5-(pyridin-1-ium-3-yl)-5H-1,2,3,4-tetrazol-5-ide (ptz). The components are linked into a two-dimensional layer by a combination of O—H⋯O, O—H⋯N, N—H⋯O and N—H⋯N hydrogen bonds parallel to the (10 Inline graphic ) plane. Layers comprising alternating rows of tma and ptz are linked into a three-dimensional network by C—H⋯O and π–π interactions between tma and tetrazolate rings [centroid–centroid distance = 3.763 (2) Å], and between pyridinium and tetrazolate rings [centroid–centroid distance = 3.745 (2) Å].

Related literature

For crystal engineering studies involving the components of the title compound, see: Lin et al. (2005 ▶); Luo et al. (2005 ▶); Yang et al. (2011 ▶).

Experimental

Crystal data

C₆H₅N₅·C₉H₆O₆
M _r = 357.29
Triclinic,
a = 7.6596 (8) Å
b = 8.7374 (9) Å
c = 11.3931 (11) Å
α = 94.336 (2)°
β = 95.584 (1)°
γ = 98.465 (2)°
V = 747.46 (13) Å³
Z = 2
Mo Kα radiation
μ = 0.13 mm⁻¹
T = 298 K
0.16 × 0.12 × 0.10 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1997 ▶) T _min = 0.970, T _max = 0.988
7554 measured reflections
2770 independent reflections
2438 reflections with I > 2σ(I)
R _int = 0.028

Refinement

R[F ² > 2σ(F ²)] = 0.068
wR(F ²) = 0.139
S = 1.24
2770 reflections
248 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.24 e Å⁻³
Δρ_min = −0.29 e Å⁻³

Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT-Plus (Bruker, 2001 ▶); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: PLATON (Spek, 2009 ▶); software used to prepare material for publication: PLATON.

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811021490/tk2753sup1.cif

e-67-o1620-sup1.cif^{(19.1KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811021490/tk2753Isup2.hkl

e-67-o1620-Isup2.hkl^{(136KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811021490/tk2753Isup3.cml

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
N1—H1⋯N4ⁱ	0.88 (4)	2.25 (4)	2.981 (3)	141 (3)
N1—H1⋯O3	0.88 (4)	2.49 (3)	2.958 (3)	114 (3)
O1—H1A⋯O5ⁱⁱ	0.83 (5)	1.88 (5)	2.694 (3)	165 (5)
O4—H4A⋯N3ⁱ	0.92 (4)	1.73 (4)	2.635 (3)	168 (4)
O6—H6A⋯N4ⁱⁱⁱ	0.98 (4)	2.57 (4)	3.325 (3)	134 (3)
O6—H6A⋯N5ⁱⁱⁱ	0.98 (4)	1.70 (4)	2.647 (3)	163 (3)
C3—H3⋯O6^iv	0.93	2.41	3.230 (3)	147
C4—H4⋯O2^v	0.93	2.54	3.418 (4)	157

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) ; (v) .

Acknowledgments

We thank Central Chinal Normal University for supporting this study.

supplementary crystallographic information

Comment

Recently, pyridyl-tetrazole ligands have been used in the construction of metal-organic complexes (Yang, et al., 2011; Lin et al., 2005; Luo, et al., 2005). In the reaction of trimesic acid (tma), 5-(3-pyridyl)tetrazolate (ptz) and CdSO₄ under hydrothermal conditions, we have unexpectedly obtained the title compound, (I), and determined its crystal structure.

In (I), the asymmetric unit comprises a neutral trimesic acid (tma) molecule and a 5-(3-pyridinium)tetrazolate (ptz) zwitterion (Fig. 1). In tma, the three carboxyl hydrogen atoms were readily found from the difference maps. This, coupled with the disparity in the C—O bond distances, confirms its neutral composition. The three carboxyl groups are twisted away from the central benzene plane forming dihedral angles of 6.59 (17) °, 16.12 (16) ° and 7.10 (16) ° between the groups containing the O1, O3 and O5 atoms, respectively. In the ptz zwitterion, the tetrazole ring is twisted away from the adjacent benzene ring with the dihedral angle between them being 16.38 (16) °.

In the crystal packing of (I), the component species are linked into a two-dimensional array running parallel to the (101) plane by a combination of O—H···O, O—H···N, N—H···O and N—H···N hydrogen bonds (Fig. 2 and Table 2). The layer can be analysed in terms of two sub-structures. Firstly, by the O1—H1A···O5 (x, y - 1, z) and N—H1···N4 (x, 1 + y, z) hydrogen bonds which link tma and 3-ptz ions into one-dimensional chains along the c axis (Fig. 2). Secondly, adjacent chains are joined together by the N1—H1···O3, O4—H4A···N3 (x, 1 + y, z) and O6—H6A···N5 (1 + x, 1 + y, 1 + z) hydrogen bonds, resulting in the formation of a two-dimensional layer parallel to the (101) plane (Fig. 2). Further analysis indicates that these adjacent layers are linked into the three-dimensional network by a combination of a C4—H4···O2 (-x,1 - y,1 - z) contacts and two π–π interactions (Fig. 3), one occurs between symmetry-related tma and tetrazolate rings [centroid distance: 3.763 (2) Å, dihedral angle: 11.10 (15) °, symmetry code: 1 - x, 1 - y, 1 - z], and the other occurs between symmetry-related pyridinium and tetrazolate rings [centroid distance: 3.745 (2) Å, dihedral angle: 16.38 (16)°, symmetry code: -x, 1 - y, 1 - z].

Experimental

All the reagents and solvents were used as obtained without further purification. Equivalent molar amounts of trimesic acid, 5-(3-pyridyl)tetrazole and CdSO₄ were reacted under hydrothermal conditions. The mixture was sealed in a 23 cm³ Teflon-lined stainless steel container. The temperature was kept at 433 K for 4 days and cooled to room temperature at the rate of 5 K /h. Colourless crystals of (I) were obtained and separated manually.