The coordination chemistry of the multidentate Schiff-base ligands 2,5-bis(3-methylpyrazinyl)-3,4-diaza-2,4-hexadiene (L5) and 2,5-bis(pyrazinyl)-3,4-diaza-2,4-hexadiene (L6) with inorganic Ag(I) salts has been investigated. Six new Ag(I)-coordination polymers were prepared by solution reactions and fully characterized by infrared spectroscopy, elemental analysis, thermogravimetric analysis, and single-crystal X-ray diffraction. [Ag(L5)]ClO4.0.5CH(3)OH (1, orthorhombic, Fdd2; a = 20.0896(11) Angstrom, b = 48.224(3) Angstrom, c = 7.8432(4) Angstrom, Z = 16), [Ag(L5)]PF6.0.5CH(3)CH (2, orthorhombic, Fdd2; a = 20.7255(11) Angstrom, b = 46.166(2) Angstrom, c = 8.4332(4) Angstrom, Z = 16), [Ag(L5)]SbF6.0.5CH(3)OH (3, orthorhombic, Fdd2; a = 21.5481 (11) Angstrom, b = 45.196(2) Angstrom, c = 8.7331(4) Angstrom, Z = 16), and [Ag(L5)](BF4).0.5CH(3)OH (4, orthorhombic, Fdd2; a = 19.8897(11) Angstrom, b = 48.358(3) Angstrom, c = 7,7491(5) Angstrom, Z = 16) were obtained by combination of L5 with AgClO4.xH(2)O, AgPF6, AgSbF6, and AgBF4, respectively, in a methylene chloride/methanol mixed solvent system. Compounds 1-4 are isostructural and feature noninterpentrating three-dimensional zeolite-like networks. [Ag4(L6)(4)](PF6)(4).CHCl3 (5, tetragonal, P4c2; a = 16.1067(3) Angstrom, b = 16.1067(3) Angstrom, c = 14.4935(5) Angstrom, Z = 2) was generated from the reaction of L6 with AgPF6 in a chloroform/ethanol mixed solvent system. It forms with a unique one-dimensional nanometer-tube that can be considered a new polymeric motif based on the {AgN5} coordination sphere. The tubes are square with crystallographic dimensions of 10.3 x 10.0 Angstrom. The tubes are further linked together through weak interpolymer C-H... F hydrogen bonding interactions into a novel H-bonded three-dimensional network containing square tubes, in which uncoordinated PF6- counterions and chloroform guest molecules are located. Compound 6 ([Ag(mu-C6H6N2O)](SO3CF3), monoclinic, P2(1)/c; a = 12.3435(6) Angstrom, b = 20.3548(10) Angstrom, c = 9.0861(5) Angstrom, Z = 8) was obtained by combination of AgSO3CF3 and L6 in a methylene chloride/benzene mixed solvent system. In 6, 2-acetylpyrazine, which was generated from the hydrolysis reaction of L6 in the presence of CF3SO3- and a small quantity of water in solvent, chelates the Ag(I) centers through the carbonyl O-clonor, and the vicinal pyrazine N-donor, furthermore, uses the para-N atoms to link other Ag(l) centers into one-dimensional zigzag chains. The triflate anions link the chains into a three-dimensional network by somewhat long Ag...O contacts.