Reactions of a mixed dioxa-diaza macrocycle 5,6,14,15-dibenzo-1,4-dioxa-8,12-diazacyclopentadeca-5,14-diene ( L) and various sodium salts NaX (X = picrate, ClO 4, BF 4, PF 6, SCN and BPh 4) in methanol afford the ion-pair compounds containing the protonated macrocyclic ligand as the cation, with the anion from the sodium salt as a counterion. The new compounds were identified and characterized on the basis of elemental analysis, spectroscopic studies (IR, 1H NMR and MS), conductivity data and X-ray structure analysis. The mode of ligand protonation, as well as the hydrogen bond network which stabilizes the binding site of the proton in the protonated macrocyclic species, depend on the sodium salt used. It was found that the proton-to-ligand ratio is 1:1 in the picrate salt ( 1), 1:2 in the perchlorate ( 2), tetrafluoroborate ( 3), hexafluorophosphate ( 4) and thiocyanate ( 5) salts, and 2:3 in the tetraphenylborate salt ( 6), which was converted by recrystallization in acetonitrile into the 1:1 salt ( 7). In the 1:1 proton:ligand compounds, [H( L)]X, the intraligand monoprotonation occurs in two modes: the proton is either bound to one of the nitrogen atoms ( 1) or is disordered between two nitrogen atoms ( 7). In the compounds with 1:2, [H( L) 2]X, and 2:3, [H 2( L) 3](X) 2, proton-to-ligand ratios, there is interligand protonation where one proton is located between nitrogen atoms from two macrocyclic molecules ( 2– 5) or two protons are shared between nitrogens from three ligand moieties ( 6). Crystallographic and infrared spectroscopic data indicate some differences in location of the proton between the nitrogen atoms in the monoprotonated ligand salts 2– 5.