Abstract: | Crystallization of the title compound, di‐μ‐pyridazine‐1κ2N:2κ2N′‐bis(2,3‐dihydro‐3‐oxobenzisosulfonazolato‐κN)silver(I)], Ag2(C7H4NO3S)2(C4H4N2)2], from acetonitrile yields both monoclinic, (I), and triclinic, (II), polymorphs. In both forms, the silver(I) ions have a slightly distorted trigonal AgN3 coordination geometry and are doubly bridged by two neutral pyridazine (pydz) ligands, generating a centrosymmetric dimeric structure. The saccharinate (sac) ligands are N‐coordinated. The dihedral angles between the sac and pydz rings are 8.43 (7) and 7.94 (8)° in (I) and (II), respectively, suggesting that the dimeric molecule is nearly flat. The bond geometry is similar in both polymorphs. In (I), the dimers interact with each other via aromatic πsac–πpydz stacking interactions, forming two‐dimensional layers, which are further crosslinked by weak C—H?O interactions. Compound (II) exhibits similar C—H?O and π–π interactions, but additional C—H?π and π?Ag interactions help to stabilize the packing of the dimers. |