A ladder-type coordination polymer constructed from two macrocyclic units - calix[4]arene tetracarboxylate and azamacrocyclic nickel(ii) complexElectronic supplementary information (ESI) available: Details for preparation, crystal structure refinement, XRPD patterns of the polycrystalline sample, IR and solid-state reflectance spectra of the compounds, comparison of the crystallographic data for the perchlorate salts of the parent macrocyclic cations and the parameters of hydrogen bonds. CCDC 93

The crystal structures of a new type of coordination polymer formed by the high-spin form of a hexaazamacrocyclic nickel( ii ) complex and a lower rim calix[4]arene tetracarboxylate trianion ( 2 ) as well as the perchlorate salt of the low-spin form of this macrocyclic cation ( 1 ) are reported. The porosity of the network is characterized by the presence of polar and non-polar voids formed by carboxylate substituents/azamacrocyclic cations and aromatic/ tert -butyl substituents of the calix[4]arene, respectively. Spatially-separated polar channels and non-polar voids were shown to coexist in the crystal of a new type of coordination polymer formed by a hexaazamacrocyclic nickel( ii ) cation and a lower rim substituted calix[4]arene tetracarboxylate trianion.