This work presents eight coordination assemblies based on divalent metal ions (M = CoII, CuII, ZnII, and CdII), dicyanamide anion (N(CN)2â, dca), and two isomeric bent dipyridyl coligands (L), namely, 2,5-bis(3-pyridyl)-1,3,4-oxadiazole (3-bpo) and 2,5-bis(4-pyridyl)-1,3,4-oxadiazole (4-bpo). In the resulting crystalline materials, both bpo and dca tectons generally display the bidentate bridging fashion (except in the mononuclear species 5), extending the metal centers to afford diverse one-, two-, and three-dimensional (1-D, 2-D, and 3-D) coordination networks that are not commonly observed in MâdcaâL systems. Notably, the inclined polycatenated 2-D â 3-D framework and 3-D polyknotting network with the unique 6-connected (44.611) topology are formed for the CuIIand CdIIspecies with dca and 4-bpo. For the polymeric CoIIand CuIIcomplexes, very weak antiferromagnetic or ferromagnetic interactions are observed between the metal centers due to the μ1,5-bridging mode of dca, and their magneto-structural correlations have been discussed in detail. The ZnIIand CdIIcomplexes show solid-state fluorescent emissions at room temperature. [ABSTRACT FROM AUTHOR]