The synthesis of a novel macrotricyclic ligand (L3) containing a N 4 S 2 donor set and characterization of a protonated macrobicyclic ion with N 4 S donors ([H 2 (L2)] 2 + ) is reported. The approach to the tricyclic system differs from that used previously for the bicyclic N 4 S ligand, employing the formation of a tetraamide that reacts with sodium sulfide to effect ring closure of two nine-membered rings. Alkali ions present in the reaction mixture were found to be incorporated into the tricyclic tetraamide framework suggesting an equilibrium between Group(I) metal ions and the product L5. The reduced ligand, (L3), can maintain two configurations, syn- or anti- depending on whether the nine-membered rings are on the same or opposite sides of the cyclam ring. A detailed crystallographic analysis is presented of the ions ([H 2 (L2)] 2 + ), ([H 2 (L3)] 2 + ) and a mono-protonated lithium complex ([Li(HL3)] 2 + ). In the case of the tricyclic ions, the N-substituents on the cyclam ring adopt the anti-orientation providing examples of the unusual trans-IV cyclam ring conformation (trans-R,R,S,S) that is extremely rare.