The reaction between bis(1-pyrazolyl)sulfone (prepared in situ by the reaction between NaH, Hpz, and SOCl 2 in THF) and C 6 H 4 [C(O)(2-py)] 2 in THF catalyzed by CoCl 2 yields m-C 6 H 4 [C(pz) 2 (2-py)] 2 (1, pz= pyrazolyl, py=pyridyl) in moderate yield, along with 1-[C(pz) 2 (2-py)]-4-[C(O)(2-py)]C 6 H 4 . The potentially bitopic ligand 1 reacts with AgPF 6 to yield [Ag(1) 2 ](PF) 6 (3), regardless of the stoichiometry of reagents used in the preparation. X-ray structural analysis of this silver complex shows that two ligands bond to a silver in a κ 2 -fashion via the pyrazolyls in one C(pz) 2 (py) group in each ligand while the other is non-coordinated. The AgN 4 C chelate rings adopt a boat conformation and the silver resides in an unusual square planar coordination environment. Non-covalent forces organize the two-dimensional structure of 3 such that it approaches a layered inorganic-organic hybrid material. Reaction of C 6 H 5 [C(pz) 2 (2-py)] and AgPF 6 yields {Ag(κ 2 -C 6 H 5 [C(pz) 2 (2-py)]) 2 }(PF 6 ) (4). The structure is disordered but the ligands are bidentate, the nitrogen donor atoms are in a square planar coordination environment about the silver and the overall structure is similar to 3.