The complex [Mg(acacCN)2(H2O)2] (acacCN = 3-cyanoacetylacetonate) has been synthesized in good yield and fully characterized. It represents a versatile labile precursor for an anionic tris(ligand) complex which is crosslinked with Ag(I) to five different neutral bimetallic networks; all of them are solvates. Four of these extended structures share the same framework stoichiometry Ag[Mg(acacCN)3] and only differ in their solvent content. The co-crystallized solvent molecules decide the topological outcome of the crosslinking: the four compounds can be classified into two isomorphous 3D networks and two non-isomorphous but related 2D layer structures. The individual structures suggest preferred inclusion of dichloromethane, followed by acetone; direct competition experiments confirm these considerations. An additional coordination polymer shows the framework stoichiometry Ag2[Mg(acacCN)2(MeOH)2][Mg(acacCN)3]2; this binodal 3D network is associated with the unprecedented vertex symbol (109·1011·1013)(103·107·107·107·108·1010).
