Ammonium diamminesilver(I) bis(5-chloro-2-hydroxybenzenesulfonate) trihydrate

The reaction of silver nitrate with 5-chloro-2-hydroxybenzenesulfonic acid in the presence of ammonia yielded the title salt, (NH4)[Ag(NH3)2](C6H4ClO4S)2·3H2O. The AgI ion shows linear coordination [N—Ag—N = 175.2 (1) °]. The ammonium and diamminesilver cations, the benzenesulfonate anion and the lattice water molecules interact through an intricate network of N—H⋯O and O—H⋯O hydrogen bonds to form a three-dimensional network.

The reaction of silver nitrate with 5-chloro-2-hydroxybenzenesulfonic acid in the presence of ammonia yielded the title salt, (NH 4 )[Ag(NH 3 ) 2 ](C 6 H 4 ClO 4 S) 2 Á3H 2 O. The Ag I ion shows linear coordination [N-Ag-N = 175.2 (1) ]. The ammonium and diamminesilver cations, the benzenesulfonate anion and the lattice water molecules interact through an intricate network of N-HÁ Á ÁO and O-HÁ Á ÁO hydrogen bonds to form a three-dimensional network.

Related literature
For a review of metal arenesulfonates, see: Cai (2004).
In this study, the attempt to synthesize the silver(I) derivative of 5-chloro-2-hydroxybenzenesulfonic acid in the presence of ammonia gave instead the ammine-coordinated salt (Scheme I) in which the diamminesilver cation interacts indirectly with the 2-hydrox-5-chlorobenzenesulfonate anion through the coordinated ammine ligands in an outer-sphere type of coordination. In the salt, [Ag(NH 3 ) 2 ][NH 4 ](C 6 H 4 ClO 4 S) 2 . 3H 2 O (Fig. 1), the Ag II atom shows linear coordination [N-Ag-N 175.2 (1) °]. The ammonium and diamminesilver cations, the benzenesulfonate anion and the lattice water molecules interact through N-H···O and O-H···O hydrogen bonds to form a three-dimensional network (Table 1).

Experimental
Silver nitrate (1 mmol) and and 5-chloro-2-hydroxy-benzenesulfonic acid (1 mmol) were mixed in water (15 ml). The pH of the solution was adjusted to ca 6 by the addition of drops of ammonium hydroxide. The solution was filtered; colorless crystals were isolated after several days. The solution was shielded from light during the crystallization.

Refinement
Carbon-bound H-atoms were placed in calculated positions (C-H 0.93 Å) and were included in the refinement in the riding model approximation, with U(H) set to 1.2U(C). The hydroxy H atoms were assumed to be co-planar with the aromatic ring, and these were similarly constrained (O-H 0.84 Å) and their displacement factors were set to 1.5U eq (O). The amino H atoms were similarly constrained (N-H 0.88 Å) and their displacement factors were set to 1.5U eq (N).
The water H-atoms were located in a difference Fourier map, and were refined with distance restraints O-H 0.84±0.01 Å and H···H 1.37±0.01 Å; their temperature factors were tied by a factor of 1.5 times.