New silver(I) double salts (Ag2C2)(AgCF3CO2)8(3-pyCONH2)2(H2O)4 (1), [(Ag2C2)(AgCF3CO2)4(4-pyCONH2)(H2O)]·H2O (2), (Ag2C2)(AgCF3CO2)6(3-pyCONH2)4 (3), (Ag2C2)(AgCF3CO2)6(3-pyCN)2 (4) and (Ag2C2)(AgCF3CO2)4(4-pyCN)2 (5) (n-pyCONH2 is pyridine-n-carboxamide, n-pyCN is n-cyanopyridine; n = 3, 4) have been synthesized by the hydrothermal method. All five compounds contain polyhedral silver(I) cages each encapsulating a C22− dianion. Compounds 1, 3, 4 and 5 exhibit three-dimensional structures, whereas compound 2 is a two-dimensional network. The structure of 1 is constructed from the linkage of a branched-tree architecture via hydrogen bonds. Unlike 4 and 5, which involve the connection of n-cyanopyridine (n = 3, 4) with silver columns, 3 results from the linkage of discrete silver cages via pyridine-3-carboxamide.
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