Abstract: | A novel metal–organic framework, {Zn2Cl4(C25H24N4O4)]·4C3H7NO}n, has been synthesized solvothermally by assembling the semi‐rigid tetrahedral ligand tetrakis(pyridin‐4‐yl)oxymethyl]methane (tpom) and zinc nitrate in dimethylformamide (DMF). The crystal structure is noncentrosymmetric (P21c). Each ZnII cation has a tetrahedral coordination environment (C2 symmetry), which is formed by two chloride ligands and two pyridine N atoms from two tpom ligands. The tetrahedral tetradentate tpom linker has a quaternary C atom located on the crystallographic axis. This linker utilizes all the peripheral pyridine N atoms to connect four ZnII cations, thereby forming a wave‐like two‐dimensional sheet along the c axis. The two‐dimensional layer can be topologically simplified as a typical uninodal 4‐connected sql/Shubnikov net, which is represented by the Schläfli symbol {44,62}. Adjacent layers are further packed into a three‐dimensional structure by C—H...Cl hydrogen bonds. |