Synthesis and characterization of new coordination polymers generated from triazole-containing organic ligands and inorganic Ag(I) salts

The coordination chemistry of the triazole-containing rigid crooked tetradentate ligands 3,5-bis(4pyridyl)-4-amino-1,2,4-triazole (L,5) and 3,5-bis(3-pyridyl)-4-amino-1,2,4-triazole (L6) with inorganic Ag(l) 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, P (1) over bar; a = 6.9481(5) angstrom, b = 9.7267(6) angstrom, c = 12.8803(8) angstrom, alpha = 92.7760(10)degrees, beta = 99.1170(10)degrees, gamma = 104.4150(10)degrees, 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 x 6 angstrom and 4 x 8 angstrom, respectively. {[Ag(3)(L5)(3)](PF(6))(3)center dot(H(2)O)center dot(CH(3)OH)}(n) (2) (monoclinic, P2(1)/n; a = 10.4641(6) angstrom, b = 15.6701(8) angstrom, c = 31.1907(17) angstrom, beta = 94.8840(10)degrees, 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 x 8.0 angstrom) extending along the crystallographic a axis. {[Ag(L5)]-(ClO(4))center dot H(2)O}(n) (3) (triclinic, P (1) over bar; a = 10.3605(16) angstrom, b = 10.5224(16) angstrom, c = 15.014(2) angstrom, alpha = 89.979(2)degrees, beta = 76.656(2)degrees, gamma = 89.980(2)degrees, 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 x 8.0 angstrom) along the crystallographic a axis, in which noncoordinated ClO(4)(-) anions and H(2)O guest molecules are located. {[Ag(L6)j(ClO(4))center dot CH(3)OH}(n) (4) (monoclinic, C2/c; a = 14.1747(10) angstrom, b = 16.2713(11) angstrom, c = 15.9983(11) angstrom, beta = 114.9410(10)degrees, 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 x 7 and 18 x 4 angstrom, respectively. Uncoordinated ClO(4)(-) counterions and MeOH guest molecules are located in these channels. {[Ag(L6)(PF(6))center dot 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) angstrom, b = 16.5919(11) angstrom, c = 16.1240(10) , beta = 116.8490(10)degrees, Z = 8. Compound 5 and 4 are isostructural. {[Ag(2)(C(12)H(10)N(6))(2)](SiF(6))center dot 2H(2)O}(n) (6) (monoclinic, P2(1)/c, a = 11.3839(6) angstrom, b = 16.5163(8) angstrom, c = 7.4485(4) angstrom, beta = 95. 5450(10 degrees, 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)(2-) anions 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)(2-) counterions and water guest molecules are located.