[(E)-Oxido(pyridin-2-ylmethylidene)-amine-kappa N-2,N '][(E)-N-(pyridin-2-ylmethylidene)hydroxylamine-kappa N-2,N ']silver(I) perchlorate-bis[(E)-N-(pyridin-2-ylmethylidene)hydroxylamine-kappa N-2,N ']silver(I) (1/1)

In the title salt co-crystal, [Ag(C6H5N2O)(C6H6N2O)]ClO4 center dot[Ag(C6H6N2O)(2)], the asymmetric unit comprises a [Ag(LH)(2)](+) cation, a perchlorate anion and a neutral (LH)AgL molecule, where LH is pyridine-2-carboxaldoxime. Both silver-containing species feature N,N'-chelating LH and L ligands, which define an N-4 donor set that is highly distorted [dihedral angles between AgC2N2 chelate rings = 45.7 (3) and 44.3 (2)degrees, respectively] owing, in part, to the close approach of a neighbouring Ag atom, leading to an argentophilic interaction [Ag center dot center dot center dot Ag = 3.1868 (11) angstrom]. The molecular conformations are stabilized by intramolecular O-H center dot center dot center dot O hydrogen bonds. In the crystal, O-H center dot center dot center dot O interactions lead to supramolecular chains along [010]. Chains aggregate into layers in the ab plane, defining channels along [100] in which reside the perchlorate anions; the latter are disordered over two overlapped orientations in a 50:50 ratio.