Sulfonic acid groups with C 3ν symmetry can coordinate with metal ions to produce multidimensional structures due to their flexible coordination modes. They can also penetrate into supramolecular structures through an intriguing bridging pattern and weak interactions. Herein, a novel heterocyclic sodium sulfonate supramolecular structure, namely [Na(Pyr-SO 3 )(H 2 O)] n where Pyr-SO 3 H is pyrazine sulfonic acid, is synthesized by utilizing NaBF 4 to coordinate with the P–SO 3 H ligand through the solvent evaporation method. The single crystal X-ray diffraction (XRD) data indicate that the as-formed structure belongs to the Pbca space group. Additional properties are characterized by powder XRD, thermal analysis, and solid-state fluorescence. In particular, the introduction of a soft alkali metal ion can coordinate with the oxygen atom of the sulfonate ligand and form a Na–O bridging configuration that can not only significantly improve the pyrazine sulfonic acid ligand coordination ability, but also provide a reference for the extended study of functional sulfonate polymers in the future. Electronic supplementary material Supplementary material is available for this article at 10.1134/S0022476621110172 and is accessible for authorized users.