Bis[μ-1,4-bis­(4,5-dihydro-1H-imidazol-2-yl)benzene-κ2 N 3:N 3′]silver(I) dinitrate dihydrate

Hua Sun; Chun-Xia Ren; Bin Shen; Zhi-Qiang Liu; Yu-Qiang Ding

doi:10.1107/S1600536808001633

. 2008 Jan 30;64(Pt 2):m427–m428. doi: 10.1107/S1600536808001633

Bis[μ-1,4-bis(4,5-dihydro-1H-imidazol-2-yl)benzene-κ² N ³:N ^3′]silver(I) dinitrate dihydrate

Hua Sun ^a, Chun-Xia Ren ^a, Bin Shen ^a, Zhi-Qiang Liu ^a, Yu-Qiang Ding ^a,^*

PMCID: PMC2960425 PMID: 21201371

Abstract

The reaction of 1,4-bis(4,5-dihydro-1H-imidazol-2-yl)benzene (bib) with silver(I) nitrate in a 1:1 molar ratio generates the metallacyclic title complex, [Ag₂(C₁₂H₁₄N₄)₂](NO₃)₂·2H₂O, in which the bib ligand displays a cis configuration. Each bib ligand acts as a bidentate bridging ligand connecting a pair of Ag^I ions to form a [2 + 2] metallamacrocycle in which the Ag⋯Ag distance is 6.77 (2) Å. Each Ag^I ion has weak contacts (2.91 Å) with the nitrate anion. The uncoordinated water molecules make hydrogen bonds with nitrate O atoms, forming chains. The H atoms attached to the uncoordinated nitrogen interact with these chains through N—H⋯O hydrogen bonds, forming layers parallel to the ( Inline graphic 11) plane.

Related literature

For related literature, see: Moulton & Zaworotko (2001 ▶); Nardelli (1999 ▶); Ren, Ye, He et al. (2004 ▶); Ren, Ye, Zhu et al. (2004 ▶); Ren et al. (2007 ▶); Toh et al. (2005 ▶); Zhang et al. (2005 ▶).

Experimental

Crystal data

[Ag₂(C₁₂H₁₄N₄)₂](NO₃)₂·2H₂O
M _r = 804.34
Triclinic,
a = 10.3562 (19) Å
b = 11.053 (2) Å
c = 13.282 (2) Å
α = 97.496 (3)°
β = 95.354 (3)°
γ = 101.613 (3)°
V = 1465.3 (4) Å³
Z = 2
Mo Kα radiation
μ = 1.40 mm⁻¹
T = 273 (2) K
0.30 × 0.25 × 0.20 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1998 ▶) T _min = 0.678, T _max = 0.767
7650 measured reflections
5316 independent reflections
3797 reflections with I > 2σ(I)
R _int = 0.017

Refinement

R[F ² > 2σ(F ²)] = 0.049
wR(F ²) = 0.143
S = 0.92
5316 reflections
397 parameters
3 restraints
H-atom parameters constrained
Δρ_max = 2.17 e Å⁻³
Δρ_min = −0.82 e Å⁻³

Data collection: SMART (Bruker, 1998 ▶); cell refinement: SAINT (Bruker, 1998 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEPIII (Burnett & Johnson, 1996 ▶), ORTEP-3 for Windows (Farrugia, 1997 ▶) and PLATON (Spek, 2003 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808001633/dn2312sup1.cif

e-64-0m427-sup1.cif^{(23.7KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808001633/dn2312Isup2.hkl

e-64-0m427-Isup2.hkl^{(260.3KB, 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
N1—H1⋯O6	0.86	2.12	2.980 (6)	173
N1—H1⋯O5	0.86	2.46	3.029 (6)	124
N3—H3⋯O1	0.86	2.13	2.915 (7)	151
N3—H3⋯O2	0.86	2.64	3.143 (6)	119
N6—H6⋯O1W	0.86	2.13	2.912 (6)	150
N8—H8⋯O4ⁱ	0.86	2.33	3.073 (7)	145
O1W—H11W⋯O2ⁱⁱ	0.85	2.12	2.852 (6)	144
O1W—H12W⋯O5ⁱ	0.85	2.04	2.888 (7)	178
O2W—H21W⋯O1	0.85	2.22	3.021 (7)	157
O2W—H22W⋯O6	0.85	2.21	2.973 (7)	150

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

Acknowledgments

This work was generously supported by the National Natural Science Foundation of China (Nos. 20571033 and 20701016).

supplementary crystallographic information

Comment

Controlled assembly and crystallization of supramolecular isomers and polymorphs are an interesting challenges in the field of supramolecular chemistry and crystal engineering (Moulton et al., 2001). One of the simplest example of such supramolecular isomerism may be a discrete molecule forming a one-dimensional polymer assembled in a 1/1 metal-ligand stoichiometry(Toh et al., 2005; Zhang et al., 2005). In our previous work, we have designed and synthesized a number of such metal complexes, including silver(I) complexes with a V-shaped ligand 1,3-bis(4,5-dihydro-1H-imidazol-2-yl)benzene (Ren, Ye, He et al., 2004; Ren, Ye, Zhu et al., 2004; Ren et al., 2007) which has four potential coordinated sites with differently binding abilities. To gain more insight into the structural variation of this type of silver(I) complexes, we became interested in a new imidazole-like ligand 1,4-bis(4,5-dihydro-1H-imidazol-2-yl)benzene (bib). Here, we present the syntheses and structural characterizations of a new [2:2] metallocyclic silver(I) complexes, namely [Ag₂(bib)₂](NO₃)₂.2H₂O.

The crystal structure of the title complex consists of dimeric [Ag₂(bib)₂]²⁺ cations, as well as NO₃^- counter anion and lattice water in the solid state. As shown in Fig. 1, each pair of Ag^I ions in the title complex are coordinated by two nitrogen atoms from two different bib ligands resulting in a [2:2] 18-membered metallocycle with a Ag(1)···Ag(2) distance of 6.77 Å. The two bib ligands, acting in a cis, cis mode, are organized in a head-to-tail fashion and joined together by two silver ions through coordination bonds to give the metallocycles. All the Ag—N bond distances are from 2.078 (4) to 2.104 (4) Å, and agree with values found in the literature(Ren et al., 2004a, 2004b, 2007). The bond angles around the Ag^I ion are 164.4 (2) /% and 166.5 (2) /%.

The lattice water molecules form hydrogen bonds with nitrate oxygen atoms yielding chains. The H atoms attached to the uncoordinated nitrogen interact through N—H···O hydrogen bonds with these chains forming layers parallel to the (-1 1 1) plane. (Table 1, Fig. 2).

Experimental

All the reagents and solvents employed were commercially available and used as received without further purification.

Synthesis of Ligand bib. 1,4-Benzenedicarboxylic acid (2.31 g, 13.9 mmol), ethylenediamine (3.70 ml, 50 mmol), ethylenediamine dihydrochloride (6.64 g, 50 mmol) and toluene-p-sulfonic acid (0.208 g, 1.09 mmol) were added to the solvent of ethylene glycol (20 ml), and the mixture solution was refluxed for 3 h. About half of the ehylene glycol solvent was then slowly removed by distillation. The residue was dissolved in a mixture of water (40 ml) and concentrated HCl (11M, 3 ml). The addition of 50% aqueous NaOH gave a yellow precipitate that was purified by recrystallization. The ligand bib was obtained in 89% based on 1,4-benzenedicarboxylic acid (ca 2.68 g). Anal. calc. for C₁₂H₁₄N₄: C, 67.27; H, 6.59; N, 26.15%. Found: C, 67.13; H, 6.87; N, 26.04%.

Synthesis of [Ag₂(bib)₂](NO₃)₂.2H₂O. To a solution of AgNO₃ (0.169 g, 1 mmol) in MeCN-H₂O (v/v 1:1), an aqueous solution (2 ml) of bib (0.214 g, 1 mmol) was added. The pale-yellow solution was allowed to stand at room temperature in air avoiding illumination for a few days by slow evaporation. Colourless prismatic crystals of the title complex were obtained, which were collected by filtration washed with aqueous MeCN and dried in a vacuum desiccator over silica gel (ca 0.108 g, 27% yield based on AgNO₃). Anal. calc. for C₂₄H₃₂Ag₂N₁₀O₈. Main IR bands (KBr, cm_-1): 3340m, 2968w, 2887w, 1615m, 1567m, 1510m, 1473m, 1365 s, 1279 s, 1184m, 1049w, 983w, 693w, 576w, 528w.