Three saccharinate salts (2-aminopyrimidine): (saccharin) (1), (4-phenylthiazol-2-amine): (saccharin) (2), and (2-methylquinoline): (saccharin) (3) were prepared and structurally characterized by X-ray crystallography. Salt 1 crystallizes in the monoclinic, space group P2(1)/c, with a = 7.1782(9) A, b = 13.5105(16) A, c = 12.2251(12) A, β = 93.3410(10)°, V = 1183.6(2) A3, Z = 4. Compound 2 crystallizes in the triclinic, space group P-1, with a = 7.4584(7) A, b = 8.6930(9) A, c = 12.9179(14) A, α = 108.952(2)°, β = 91.7510(10)°, γ = 97.2280(10)°, V = 783.57(14) A3, Z = 2. Compound 3 crystallizes in the monoclinic, space group P2(1)/c, with a = 7.781(8) A, b = 19.4209(19) A, c = 10.9719(12) A, β = 107.7390(10)°, V = 1579.2(16) A3, Z = 4. The different hydrogen bonding interaction modes of the saccharinate anions and the cations lead to 3D network structure, 3D staircase structure, and 3D ABAB layer structure for 1, 2, and 3 respectively. Despite variations in the cation shape on the aromatic N–heterocyclic compounds, there all existed strong intermolecular N–H⋯O(carbonyl) hydrogen bonds. In compounds 1, and 3 the N+–H⋯O interaction between the N+–H group of the cation and the C=O group of the saccharinate anion is the most important interaction in this family of salts. However, in 2, there was a N–H⋯O interaction between the amino proton and the C=O group of the saccharinate anion. At the next level, the aromatic C–H proton interacts with the sulfonyl O atom. There are also π–π interactions in compounds 1–2, there is CH3–π interaction in 3. Under these interactions the three compounds exhibit synthons I–III respectively. These interactions are responsible for the high-yielding supramolecular assembly of N-containing aromatic bases and the saccharinate into salts. Due to the collective weak interactions, the complexes displayed 3D structure.