We achieved two novel coordination polymers hydrothermally. One consists of 5-connected 2D thick layers with {4(8).6(2)} topology. Adjacent layers interlock each other in AB fashion, affording a rare (2D -> 3D) polycatenated array. The other exhibits a two-fold interpenetrated 3D bnn topology. The relative orientation of common square-pyramidal 5-connected nodes is crucial in defining their topological structures.
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