To explore the potential of cationic cobaltammine as anion receptor, single crystals of cis-diazidobis(ethylenediamine)cobalt(III) saccharinate have been obtained by slowly mixing separately dissolved solutions of [cis-Co(en)2(N3)2]NO3 and NaC7H4SO3N in aqueous medium in nearly 1:1 molar ratio. Elemental analyses, solubility product measurement, molar conductance studies and spectroscopic techniques (IR, UV/Visible, 1H and 13C NMR) were employed for characterizing the complex salt. The complex salt crystallized in the triclinic space group P with cell dimensions a = 7.2638 (15) Å, b = 11.424 (2) Å, c = 11.953 (2) Å, Z = 2, V = 894.8 (3) Å3, R1 = 0.0401 and wR2 = 0.0910. Single crystal X-ray structure determination revealed supramolecular assemblies via hydrogen bonding network between ionic groups and NH groups of coordinated ethylenediamine molecules i.e., second-sphere coordination.