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The structure of the title complex, (C 10 H 10 N 4 )(C 10 H 9 N 4 )[Mo(CN) 8 ]·4H 2 O, consists of 4,4′-diazenediyldipyridinium and (4-pyridyldiazen­yl)pyridinium cations disordered over the same site, an [Mo(CN) 8 ] 3−  anion and four uncoordinated water mol­ecules. The cations (crystallographic symmetry, 2) and the [Mo(CN) 8 ] 3−  anion (crystallographic symmetry, 222) are arranged in an alternating fashion, forming a two-dimensional layered structure through hydrogen bonds. Hydrogen bonds, π–π stacking inter­actions (shortest distance = 4.7872 Å) and van der Waals forces between adjacent layers generate a three-dimensional supra­molecular structure.

4,4′-Diazenediyldipyridinium (4-pyridyldiazenyl)pyridinium octacyanidomolybdate(V) tetrahydrate