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In the present research, bis(Pyridinium-4-carbaldehyde thiosemicarbazone) hexafluorophosphate, nitrate (1) have been prepared by protonation of 4-Formylpyridine thiosemicarbazone (4fpytsc, 2). The compound 1 and the starting thiosemicarbazone have been well characterized and their molecular and crystal structures were studied by single-crystal X-ray diffraction. The supramolecular assembly of each crystal is also analyzed and discussed.