New coordination compounds based on 1,3,5-benzenetricarboxylate (btc3−) and complex cations of copper(II) and nickel(II) with monodentate ligands {{[Cu(py)3]3(btc)2}·4,5H2O} n (1) and {[Ni(py)3(H2O)]3(btc)2} n (2) were obtained. The molecular and crystal structures of these compounds and their isomorphism were determined by X-ray diffraction analysis. Crystals of 1 and 2 are characterized by a layered structure due to the stacking of two-dimensional coordination-polymer layers interacting with each other through C-H…π non-covalent interactions and C-H…O weak hydrogen bonds. It is shown that these compounds are potentially highly porous materials with coordinatively unsaturated metal ions (Lewis acid sites).