The synthesis and X-ray characterisation of four isomeric dipyridyl ketone oxime ligands, 4,49-dipyridyl ketone oxime, L 44 , 3,39-dipyridyl ketone oxime, L 33 , 2,4-dipyridyl ketone oxime, L 24 and 2,3-dipyridyl ketone oxime, L 23 is described. X-ray structural characterisation of the precursor ketones 3,39-dipyridyl ketone, L1, and 2,4-dipyridyl ketone, L2, is also reported for comparison. Four AgCF 3 SO 3 complexes of the dipyridyl ketone oxime ligands were prepared and structurally characterised, [Ag(L 44 ) 2 ](CF 3 SO 3 ), 1, ' , 3, and [Ag 2 L 23 (CF 3 SO 3 ) 2 ] ' , 4. The structural role of the CF 3 SO 3 2 anion in the formation of Ag(I) coordination polymer networks, together with the effect of the varying pyridyl substitution patterns of L 44 , L 33 , L 24 and L 23 was investigated. In 1 the CF 3 SO 3 2 anion was unbound and disordered. It was encapsulated in the channels of a honeycomb 3D H-bonded structure. In 2 the CF 3 SO 3 2 anion remained unbound, being encapsulated within the centre of a helical polymer chain. In 3 the CF 3 SO 3 2 anion was weakly bound to the Ag(I) ion and as such decorated the side of a bowed 1-D chain. The two different CF 3 SO 3 2 anions in 4 adopted a range of binding modes from monodentate, bismonodentate to tris-monodentate with the Ag(I) ions and gave rise to the formation of an unusual CF 3 SO 3 2 bridged 2-D network.