The coordination polymers [AgPF6(Me4Pyz)2] (I) and [AgPF6(2,3-Et2Pyz)2] (II) were synthesized, and their structures were determined. Crystals of I are monoclinic, space group C2/c, a = 10.213(2) Å, b = 16.267(3) Å, c = 12.663(3) Å, β = 92.90(3)°, V = 2102.1(7) Å3, ρcalcd = 1.660 g/cm3, Z = 4. The structure of I is built of polymeric zigzag [Ag(C8H12N2)]∞+ chains and octahedral [PF6] anions. The coordination polyhedron of the Ag+ ion is a flat triangle. Crystals of II are tetragonal, space group P\documentclass[12pt]{minimal}
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$$\end{document}2(1)/c,a = b = 10.641(1) Å, c = 18.942(1) Å, V = 2144.6(2) Å3, ρcalcd = 1.627 g/cm3, Z = 4. In the structure of II, 2D cationic layers of fused square rings exist; the rings consist of four Ag+ cations linked by four bridging ligands of diethylpyrazine Et2Pyz. The coordination polyhedron of the Ag+ ion is an irregular four-vertex polyhedron.