The reaction of Ag2(Fod)2(OH2) (H-Fod = 2,2-dimethyl-6,6,7,7,8,8,8-heptafluoro-3,5-octanedione) and the thioether macrocycles aneS4 or aneS3 affords either a one-dimensional coordination polymer [Ag2(Fod)2(aneS4)]∞ or a discrete mononuclear complex Ag(Fod)(aneS3), respectively. In [Ag2(Fod)2(aneS4)]∞ polymeric propagation occurs through the thioether macrocycle which bridges adjacent silver(I) centres. The diketonate Fod is coordinated in both complexes, acting as an inhibitor to coordination polymer propagation, but a significant elongation of the Ag–O distance is observed for the tBu substituted arm of the anion. In Ag(Fod)(aneS3) this is accentuated such that the diketonate acts in a monodentate, non-chelating manner. The influence of the asymmetric nature of the diketonate anion on both local coordination environment and long-range order is discussed.