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The principal building units in the title compound, [Co3(C9H3O6)2(C10H8N2)4(H2O)10]·C10H8N2·8H2O, are the linear centrosymmetric tricobalt(II) complex mol­ecules resulting from two square-pyramidal [Co(btc)(bpy)(H2O)3] entities (bpy is 4,4′-bipyridine and btc is the benzene-1,3,5-tricarboxyl­ate trianion) bridged by one trans-[Co(bpy)2(H2O)4]2+ unit. The trinuclear complex mol­ecules are assembled into infinite chains through inter­molecular O—H...N hydrogen bonds and π–π stacking inter­actions between adjacent monodentate bpy ligands. The chains and uncoordinated bpy mol­ecules are further assembled into two-dimensional open layers, which are stacked in a staggered manner to give a three-dimensional supra­molecular architecture with the solvent water mol­ecules in the cavities.

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In the title compound, [CdCl2(C18H12N6)]·3H2O, the Cd atom has a distorted square-pyramidal coordination geometry. The solvent water mol­ecules are hydrogen bonded to each other to form planar cyclic water hexa­mers, which, together with other hydrogen bonds, inter­link the Cd complex mol­ecules to give one-dimensional supra­molecular ribbons that extend along the [111] direction. The chains are assembled into two-dimensional layers parallel to (111) by π–π stacking inter­actions. Furthermore, inter­layer π–π stacking inter­actions and weak C—H...Cl hydrogen bonds complete the formation of a three-dimensional framework.
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