Synthesis and Characterization of New Coordination Polymers Generated from Triazole-Containing Organic Ligands and Inorganic Ag(I) Salts (original) (raw)

2005, Crystal Growth & Design

The coordination chemistry of the triazole-containing rigid crooked tetradentate ligands 3,5-bis(4pyridyl)-4-amino-1,2,4-triazole (L5) and 3,5-bis(3-pyridyl)-4-amino-1,2,4-triazole (L6) with inorganic Ag(I) salts has been investigated. Six new coordination polymers were prepared by solution reactions and fully characterized by infrared spectroscopy, elemental analysis, and single-crystal X-ray diffraction. {[Ag 3 (L5) 2 ](NO 3) 3 (H 2 O) 4 } n (1) (triclinic, P1 h; a) 6.9481(5) Å, b) 9.7267(6) Å, c) 12.8803(8) Å, R) 92.7760(10)°,) 99.1170(10)°, γ) 104.4150(10)°, Z) 1) was obtained by the combination of L5 with AgNO 3 in a H 2 O/CH 3 OH mixed solvent system, and features a unique two-dimensional sheet, which consists of large tetrameric and small dimeric rings. The approximate dimensions of the rings are ca. 23 × 6 Å and 4 × 8 Å, respectively. {[Ag 3 (L5) 3 ](PF 6) 3 ‚(H 2 O)‚(CH 3 OH)} n (2) (monoclinic, P2 1 /n; a) 10.4641(6) Å, b) 15.6701(8) Å, c) 31.1907(17) Å,) 94.8840(10)°, Z) 4) was generated from the reaction of L5 with AgPF 6 in a H 2 O/CH 3 OH mixed solvent system. In 2, Ag(I) centers are interlocked together by L5 ligands through two terminal N pyridine and two N triazole donors into a novel noninterpenetrating three-dimensional framework with elliptical channels (effective cross-section of ca. 12.4 × 8.0 Å) extending along the crystallographic a axis. {[Ag(L5)]-(ClO 4)‚H 2 O} n (3) (triclinic, P1 h; a) 10.3605(16) Å, b) 10.5224(16) Å, c) 15.014(2) Å, R) 89.979(2)°,) 76.656(2)°, γ) 89.980(2)°, Z) 4) was obtained by a combination of L5 with AgClO 4 in a MeOH/H 2 O mixed solvent system. In the solid state, it forms a novel noninterpenetrating three-dimensional network with rhombic channels (effective cross-section of ca. 9.0 × 8.0 Å) along the crystallographic a axis, in which noncoordinated ClO 4anions and H 2 O guest molecules are located. {[Ag(L6)](ClO 4)‚CH 3 OH} n (4) (monoclinic, C2/c; a) 14.1747(10) Å, b) 16.2713(11) Å, c) 15.9983(11) Å,) 114.9410(10)°, Z) 8) was obtained by the combination of L6 with AgClO 4 in a MeOH/H 2 O mixed solvent system. In the solid state, 4 features a novel noninterpenetrating three-dimensional framework with honeycomb-like and elliptical channels in two different crystallographic directions. Their dimensions are 8 × 7 and 18 × 4 Å, respectively. Uncoordinated ClO 4counterions and MeOH guest molecules are located in these channels. {[Ag(L6)](PF 6)‚CH 3 OH} n (5) is generated from L6 and AgPF 6 in a H 2 O/MeOH mixed solvent system and crystallizes in the space group C2/c, with a) 15.2035(10) Å, b) 16.5919(11) Å, c) 16.1240(10) Å,) 116.8490(10)°, Z) 8. Compound 5 and 4 are isostructural. {[Ag 2 (C 12 H 10 N 6) 2 ](SiF 6)‚2H 2 O} n (6) (monoclinic, P2 1 /c, a) 11.3839(6) Å, b) 16.5163(8) Å, c) 7.4485(4) Å,) 95.5450(10)°, Z) 2) was obtained by the combination of L6 ligand with AgSbF 6 in a MeOH/H 2 O solvent system. In the solid state, compound 6 adopts a noninterpenetrating two-dimensional net. Uncoordinated SiF 6 2anions and water molecules are located between the layers and further linked by extensive H-bonding systems into a three-dimensional framework. When viewed down the crystallographic [101] direction, honeycomb-like channels were found, in which SiF 6 2counterions and water guest molecules are located.