[(E)-Oxido(pyridin-2-ylmethylidene)amine-κ2 N,N′][(E)-N-(pyridin-2-ylmethylidene)hydroxylamine-κ2 N,N′]silver(I) perchlorate–bis[(E)-N-(pyridin-2-ylmethylidene)hydroxylamine-κ2 N,N′]silver(I) (1/1)

In the title salt co-crystal, [Ag(C6H5N2O)(C6H6N2O)]ClO4·[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 N4 donor set that is highly distorted [dihedral angles between AgC2N2 chelate rings = 45.7 (3) and 44.3 (2)°, respectively] owing, in part, to the close approach of a neighbouring Ag atom, leading to an argentophilic interaction [Ag⋯Ag = 3.1868 (11) Å]. The molecular conformations are stabilized by intramolecular O—H⋯O hydrogen bonds. In the crystal, O—H⋯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.

In the title salt co-crystal, [Ag(C 6 H 5 N 2 O)(C 6 H 6 N 2 O)]-ClO 4 Á[Ag(C 6 H 6 N 2 O) 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 0 -chelating LH and L ligands, which define an N 4 donor set that is highly distorted [dihedral angles between AgC 2 N 2 chelate rings = 45.7 (3) and 44.3 (2) , respectively] owing, in part, to the close approach of a neighbouring Ag atom, leading to an argentophilic interaction [AgÁ Á ÁAg = 3.1868 (11) Å ]. The molecular conformations are stabilized by intramolecular O-HÁ Á ÁO hydrogen bonds. In the crystal, O-HÁ Á ÁO 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.

Related literature
For structural diversity in the structures of silver salts, see: Kundu et al. (2010). For a related structure, see: Abu-Youssef et al. (2010).
In both silver-containing species, the pyridine-2-carboxaldoxime and the derived anion are N,N-chelating, Table 1. The Ag-N(pyridine) and Ag-N(oxime) bond lengths are systematically shorter and longer, respectively, in the neutral molecule than in the cation, Table 1, and the Ag-N4(oximate) distance is shorter compared with the Ag-N(oxime) bond lengths, Table 1. Each five-membered AgC 2 N 2 chelate ring is essentially planar with r.m.s. deviations of 0.062, 0.049, 0.080 and 0.035 Å, respectively for the N1, N3, N4 and N6-containing rings. The dihedral between the chelate rings involving the Ag1 atom is 44.3 (2)° indicating a distorted coordination geometry; the comparable angle for the Ag2containing molecule is 45.7 (3)°. The close approach of a neighbouring silver atom contributes to the distortion as the silver atoms are connected by an agentophilic Ag1···Ag2 interaction, Table 1.
The most prominent feature of the crystal packing is the formation of a supramolecular chain along

Experimental
Silver perchlorate (1 mmol) and picolinaldehyde oxime (1 mmol) was dissolved in methanol solution (10 ml). The solution was filtered and set aside, away from light, for the growth of crystals. Colourless prisms deposited after several days. The perchlorate anion is disordered over two sites of equal weight, with each of the two chlorides located on a centre of inversion. The oxygen atoms of each perchlorate anion are further disordered and assumed to have a 1:1 type of disorder.

Carbon
All Cl-O distances were restrained to 1.41±0.01 Å and the O···O distances to 2.30±0.01 Å. Each set of four oxygen atoms was restrained to have the same anisotropic displacement parameters and these were restrained to be nearly isotropic.
The final difference Fourier map had a peak at 0.91 Å from the Ag1 atom.

Figure 1
The molecular structure of (I) showing displacement ellipsoids at the 20% probability level. Each perchlorate anion has half-weight and for each, only one orientation is shown.