Counterion Influenced Metal‐Organic Frameworks of Cyclam with CuII

Abstract Cyclam is one of the simplest macrocycle that forms stable metal chelates, much explored for their material and biological applications. Varying anion shape is an effective strategy to modulate the supramolecular structure, inspite of same molecular structure. Here, we report six new complexes of cyclam with Cu II bound to counterions of different shapes viz., linear (NCS − /N 3 − ), bent (N(CN) 2 − ) or spherical (Cl − /Br − /I − ) in which the shape of the anion leads to distinctly different supramolecular structures (ladder/linear chains with linear anions), braid like (with bent anion) and 3‐D hydrogen bonded networks (with spherical anions) due to changes in the non‐covalent interactions, inspite of the same molecular structure. The variations in packing are responsible for their different thermal properties. With metallo‐cyclams being explored for their efficacy in medical and material fields, studies of this type may offer potential candidates to explore.