Tris(1H-benzimidazol-3-ium-2-ylmeth­yl)amine tris­(2,4,6-trinitro­phenolate) acetonitrile disolvate

Ying Bai; Jing-Kun Yuan; Hua Wang; Guo-Long Pan; Hui-Lu Wu

doi:10.1107/S160053681202329X

. 2012 May 31;68(Pt 6):o1922. doi: 10.1107/S160053681202329X

Tris(1H-benzimidazol-3-ium-2-ylmethyl)amine tris(2,4,6-trinitrophenolate) acetonitrile disolvate

Ying Bai ^a, Jing-Kun Yuan ^a, Hua Wang ^a, Guo-Long Pan ^a, Hui-Lu Wu ^a,^*

PMCID: PMC3379477 PMID: 22719675

Abstract

In the cation of the title salt, C₂₄H₂₄N₇ ³⁺·3C₆H₂N₃O₇ ⁻·2C₂H₃N, the three benzimidazolium ring systems are oriented to each other at dihedral angles of 10.42 (7), 23.98 (7) and 22.17 (7)°. In the crystal, the cation links to the adjacent picrate anions via N—H⋯O hydrogen bonds; one of independent acetonitrile solvent molecules is also linked to the cation via an N—H⋯N hydrogen bond.

Related literature

For background to benzimidazoles and their derivatives, see: Wilkinson (1987 ▶); Siya et al. (1992 ▶); Horton et al. (2003 ▶); Prados & Quesada (2008 ▶); Steed (2009 ▶); Aghabozorg et al. (2008 ▶). For intermolecular interactions, see: Blake et al. (2000 ▶); Bourne et al. (2001 ▶); Desiraju (2000 ▶). For our previous model studies, see: Liu et al. (2011 ▶);

Experimental

Crystal data

C₂₄H₂₄N₇ ³⁺·3C₆H₂N₃O₇ ⁻·2C₂H₃N
M _r = 1176.93
Triclinic,
a = 10.9914 (3) Å
b = 15.4620 (5) Å
c = 16.1760 (6) Å
α = 74.826 (1)°
β = 74.337 (1)°
γ = 73.299 (1)°
V = 2484.29 (14) Å³
Z = 2
Mo Kα radiation
μ = 0.13 mm⁻¹
T = 153 K
0.38 × 0.36 × 0.30 mm

Data collection

Bruker APEXII CCD diffractometer
18903 measured reflections
8608 independent reflections
6896 reflections with I > 2σ(I)
R _int = 0.016

Refinement

R[F ² > 2σ(F ²)] = 0.037
wR(F ²) = 0.127
S = 1.14
8608 reflections
769 parameters
H-atom parameters constrained
Δρ_max = 0.60 e Å⁻³
Δρ_min = −0.52 e Å⁻³

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S160053681202329X/xu5538sup1.cif

e-68-o1922-sup1.cif^{(39.6KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681202329X/xu5538Isup2.hkl

e-68-o1922-Isup2.hkl^{(421KB, hkl)}

Supplementary material file. DOI: 10.1107/S160053681202329X/xu5538Isup3.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—H1A⋯O1	0.88	1.96	2.834 (2)	173
N2—H2A⋯O15ⁱ	0.88	1.88	2.619 (2)	140
N2—H2A⋯O16ⁱ	0.88	2.27	2.952 (2)	134
N3—H3A⋯O1	0.88	2.01	2.847 (2)	158
N3—H3A⋯O7	0.88	2.33	2.905 (2)	123
N4—H4A⋯N17ⁱⁱ	0.88	2.18	2.965 (3)	148
N5—H5A⋯O1	0.88	2.28	2.836 (2)	121
N5—H5A⋯O2	0.88	2.09	2.853 (2)	144
N6—H6A⋯O8ⁱⁱⁱ	0.88	1.91	2.693 (2)	147
N6—H6A⋯O14ⁱⁱⁱ	0.88	2.30	2.945 (2)	130

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

Acknowledgments

The authors acknowledge financial support and a grant from the ’Qing Lan’ Talent Engineering Funds and Students’ Science and Technology Innovation Funds (grant No. DXS2010–040) in Lanzhou Jiaotong University. A grant from the Middle-Young Age Science Foundation (grant No. 3YS061-A25–023) and the Long Yuan ’Qing Nian’ of Gansu Province is also acknowledged.

supplementary crystallographic information

Comment

It is well known that benzimidazole is a typical heterocyclic ligand with nitrogen donor and a component of biologically important molecules (Wilkinson et al., 1987). Those compounds are environmentally friendly compounds with two high active nitrogen atoms in 1, 3-sites (Siya et al. 1992). Benzimidazoles and their derivatives being ubiquitous, quite a few of them play important roles in biological, aquatic, environmental, and industrial processes, fungicide and many other fields (Horton et al., 2003; Steed, 2009; Prados & Quesada, 2008). According to the previous report (Aghabozorg et al., 2008), H. Aghabozorg et al. focused on the proton delivery from acids, which are considered as suitable proton donors, to amines as proton acceptors. The results were production of several proton transfer ion pairs possessing some remaining donor sites applied for coordination to metallic centers in preparation of metal-organic structures. Much of the investigations show that the proton compound exist various interactions including hydrogen bondings, ion pairing, van der Waals and so on (Bourne et al., 2001; Desiraju et al., 2000; Blake et al., 2000).

In our previous model studies (Liu et al., 2011) that the bis(N-methylbenzimidazol-2-ylmethyl) aniline (MEBBA) cation attacked by a picrate anion bridge with proton transfer and formation of a novel complex, now we used similar method to synthesize the title compound. The title compound is a proton transfer compound that consists of a tris (2-benzimidazolylmethyl) amine cation, three picrate anions and diacetonitrile solvents. Three protons from three picrate anion transfer to N (double bond) fromtris (2-benzimidazolylmethyl) amine cation. The proton transfer compound is formed by picrate anions and amines can enhance the intermolecular forces between the obtained cationic and anionic fragments, and interactions described above can provide a large part of the stabilization energy of resulting self-assembly systems (Aghabozorg et al., 2008). The crystal structure is mainly stabilized by N—H—N intramolecular hydrogen bond. In this paper, the crystal unit of the title proton transfer compound be composed and the proton of the picric acid is transferred to the nitrogen atoms of the ntb (Fig. 1), and formed by tripod structrue. The angle of C9–N7–C17 is 108.15°, C8–N17–C7 is 112.55°, C8–N7–C9 is 110.46° respectively. From the crystal structure we can see that there is one ntb ligand containing three N—H bonds as hydrogen-bonding donors, each forming an N—H—O hydrogen bond with the surrounding picrate anions.

Experimental

Reagents and solvents used were of commercially available quality. To a stirred solution of tris (2-benzimidazolylmethyl)amine (0.4070 g, 1 mmol) in hot acetonitrile (10 ml) was added picrate acid (0.2291 g, 1 mmol) solution dissolved in acetonitrile (5 ml) over 4-5 h at room temperature, then the clear filtrate was collected from the resulting solution. The crystallized corresponding products were obtained from the filtrates by allowing slow evaporation of the solvent at room temperaturethe. (Yield 0.401 g, 63%). Elemental analysis found: C, 47.02%; H, 3.02%; N, 21.37%; calcd. for C46H36N81O21: C, 46.95%; H, 3.08%; N,21.42%.