Bis[μ-2-(3-pyridylmeth­yl)-2H-benzo­triazole]bis­[nitratosilver(I)]

Min Hu; Song-Tao Ma; Liang-Qi Guo; Guang-Hui Sun; Shao-Ming Fang

doi:10.1107/S160053680803479X

. 2008 Oct 31;64(Pt 11):m1473–m1474. doi: 10.1107/S160053680803479X

Bis[μ-2-(3-pyridylmethyl)-2H-benzotriazole]bis[nitratosilver(I)]

Min Hu ^a, Song-Tao Ma ^a, Liang-Qi Guo ^a, Guang-Hui Sun ^a, Shao-Ming Fang ^a,^*

PMCID: PMC2959521 PMID: 21580908

Abstract

In the title centrosymmetric binuclear Ag^I complex, [Ag₂(NO₃)₂(C₁₂H₁₀N₄)₂], each Ag^I center is coordinated by one pyridine and one benzotriazole N-donor atom of two inversion-related 2-(3-pyridylmethyl)-2H-benzotriazole (L) ligands, and an O atom of a coordinated NO₃ ⁻ anion in a distorted T-shaped geometry. This forms a unique box-like cyclic dimer with an intramolecular non-bonding Ag⋯Ag separation of 6.327 (2) Å. Weak intermolecular Ag⋯O(nitrate) interactions [2.728 (4) and 2.646 (3) Å] link the binuclear units, forming a two-dimensional network parallel to (100). Intermolecular C—H⋯O hydrogen-bonding interactions, involving the L ligands and the coordinated NO₃ ⁻ anions, link the sheets, forming a three-dimensional framework.

Related literature

For similar structures, see: Liu et al. (2006 ▶, 2007 ▶); Richardson & Steel (2003 ▶); For the synthesis of ligand L, see: Liu et al. (2008 ▶).

Experimental

Crystal data

[Ag₂(NO₃)₂(C₁₂H₁₀N₄)₂]
M _r = 760.24
Monoclinic,
a = 10.472 (2) Å
b = 8.6921 (17) Å
c = 14.656 (3) Å
β = 95.33 (3)°
V = 1328.3 (5) Å³
Z = 2
Mo Kα radiation
μ = 1.54 mm⁻¹
T = 293 (2) K
0.20 × 0.15 × 0.11 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2008 ▶) T _min = 0.749, T _max = 0.849
12799 measured reflections
2336 independent reflections
2256 reflections with I > 2σ(I)
R _int = 0.027

Refinement

R[F ² > 2σ(F ²)] = 0.036
wR(F ²) = 0.072
S = 1.11
2335 reflections
190 parameters
H-atom parameters constrained
Δρ_max = 0.96 e Å⁻³
Δρ_min = −0.70 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: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL and PLATON (Spek, 2003 ▶).

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053680803479X/su2070sup1.cif

e-64-m1473-sup1.cif^{(18.6KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S160053680803479X/su2070Isup2.hkl

e-64-m1473-Isup2.hkl^{(114.8KB, hkl)}

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

Table 1. Selected geometric parameters (Å, °).

Ag1—N4	2.253 (3)
Ag1—N1ⁱ	2.311 (3)
Ag1—O3	2.468 (3)
Ag1—O1ⁱⁱ	2.728 (4)
Ag1—O2ⁱⁱ	2.646 (3)

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N4—Ag1—N1ⁱ	131.66 (10)
N4—Ag1—O3	127.43 (11)
N1ⁱ—Ag1—O3	84.66 (11)

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

Table 2. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C5—H5⋯O2ⁱⁱⁱ	0.93	2.59	3.365 (3)	141
C6—H61⋯O2^iv	0.97	2.48	3.416 (5)	161

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Symmetry codes: (iii) Inline graphic ; (iv) .

Acknowledgments

This work was supported by the start-up fund for PhDs in Natural Scientific Research of Zhengzhou University of Light Industry (grant No. 2006BSJJ001 to SMF). We also thank Dr Chun-Sen Liu for helpful discussions and valuable suggestions.

supplementary crystallographic information

Comment

The structures of five N-containing bis-heterocyclic ligands bearing 1-substituted benzotriazole subunits, such as 1-(2-pyridylmethyl)-1H-benzotriazole and its binuclear Cu^II, Pd^II, and Ag^I complexes, have been published previously (Richardson & Steel, 2003). As part of a study on the coordination possibilities of benzotriazole-based ligands with different N-substituted positions in the self-assembly process of coordination complexes, we synthesized a nonplanar flexible ligand based on a 2-substituted benzotriazole subunit and a pendant pyridyl group, namely 2-(3-pyridylmethyl)-2H-benzotriazole (L). Ligand L was then used to construct the title compound, (I), by the reaction of L with AgNO₃.

The structure of compound (I) consists of a centrosymmetric binuclear unit compossed of two L ligands, two Ag^I centers, and two coordinated NO₃^- anions (Fig. 1). The intramolecular non-bonding Ag···Ag separation is 6.327 (2) Å. Each Ag^I center adopts a distorted T-shaped geometry (Table 1) formed by one O atom of a NO₃^- anion and two N-donor atoms; one from the benzotriazole ring system of one L ligand, and the other one from the pendant pyridine ring of another L ligand.

In this case the 16-membered dimetallocyclic ring is far from planar as a result of the presence of the tetrahedral methylene group of the L ligand. All the Ag—O and Ag—N bond distances are in the normal range found for similar complexes (Liu, Chen et al., 2006; Liu, Li et al., 2007).

In the crystal structure adjacent discrete binuclear [Ag(L)(NO₃)]₂ units are further assembled into one-dimensional chains by intermolecular Ag···O interactions [Ag1···O1ⁱⁱ = 2.728 (4) Å and Ag1···O2ⁱⁱ= 2.646 (3) Å; symmetry code ii: -x + 1, y - 1/2, -z + 1.5, see Table 1]. The net result is a two-dimensional network running parallel to the (100) plane (Fig. 2). In addition, the crystal structure of (I) also contains intermolecular C—H···O hydrogen-bonding interactions (Table 2) between the L ligands and the coordinated NO₃^- anions that interlink the two-dimensional sheets to form a three-dimensional framework.

We are currently exploring the extension of this study to other 2-substituted benzotriazole-based bis-heterocyclic ligands with bulky aromatic pendant groups, such as acridine and quinoline, and their metal-organic coordination complexes with may have potentially useful properties.

Experimental

The ligand 2-(3-Pyridylmethyl)-2H-benzotriazole (L) was synthesized according to the modified method reported in the literature (Liu, Sun et al., 2008). Benzotriazole (0.26 g, 2.2 mmol), 3-(chloromethyl)pyridine hydrochloride (3-picolyl chloride hydrochloride) (0.33 g, 2 mmol), and potassium carbonate (1.52 g, 11 mmol) were added to 50 ml of CH₃CN. The mixture was stirred at rt for ca 1 h before being heated at reflux for 24 h, with vigorous stirring. A beige precipitate was obtained, filtered off and rinsed with CH₃CN. The solvent was removed from the filtrate, and the beige product obtained was taken up in CHCl₃ and washed three times with H₂O, before being dried over anhydrous MgSO₄. Ligand (L) was obtained as a yellow powder and purified by recrystallization from CHCl₃/hexane [Yield: ca 40% (based on 3-(chloromethyl)pyridine hydrochloride)]. Elemental analysis calculated for (C₁₂H₁₀N₄): C 68.56, H 4.79, N 26.65%; found: C 68.61, H 4.8, N 26.55%. Complex (I) was prepared by adding a solution of AgNO₃ (0.1 mmol) to a mixture of ligand L (0.1 mmol) in CH₃OH (15 ml) and CH₃CN (5 ml). A yellow solid formed which was filtered off and the resulting solution was kept at rt. Yellow crystals of complex (I), suitable for X-ray analysis, were obtained by slow evaporation of the solvent after several days. Yield: ~30%. Elemental analysis calculated for (C₁₂H₁₀AgN₅O₃): C 37.92, H 2.65, N 18.42%; found: C 37.81, H 2.70, N 18.34%.