We show in this presentation that zinc metallated porphyrins containing nitrophenyl groups form layered coordination polymers with predictable topology. These polymers are built on a new coordination synthon, zinc...nitro recognition. The bonding in this recognition is defined by short Zn...O contacts, octahedral geometry at Zn, and differences in the bond length and thermal vibrations of bound and unbound O-atoms of the nitro group. When monodentate ligands stronger than nitro groups are introduced into the system, new types of extended solids are formed. Use of linear bidentate ligands led to the formation of dimers that exhibited quadrupolar or octupolar symmetry depending on the mutual superposition of the two porphyrin rings in the dimer.