A series of Cu^II coordination polymers with different topologies, namely [CuL(L¹)]·2 H₂O (1), [CuL_1.5(L²)]·3 H₂O (2), [CuL(L³)]·3 H₂O (3) and [Cu₂L_2.5(L⁴)(H₂O)]·10 H₂O (4) [L = 1,1'‐(1,4‐butanediyl)bis(imidazole), H₂L¹ = fumaric acid, H₂L² = 1,1'‐ferrocenedicarboxylic acid, H₂L³ = succinic acid, and H₄L⁴ = pyromellitic acid], are presented. Different polymeric frameworks are obtained by varying the polycarboxylate anions. These include the threefold interpenetrated diamond structure of 1, the rare twofold interpenetrated 4⁶6⁴ network of 2, and two planar four‐connected networks of 3 and 4, which display an unusual Archimedean‐type (6⁵8)(6⁴8²) net containing two different types of nodes and a (56⁴8)(5²6²8²)₂(68 ⁴10)(5⁴6²) net containing four different types of nodes, respectively. Thermogravimetric analysis (TGA) curves of 1, 2, 3, and 4 exhibit three similar weight‐loss stages. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)

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