Attempts of the synthesis of ionic (NH₄)(BH₃NH₂BH₂NH₂BH₃) via a metathetical approach resulted in a mixture of the target compound and partly dehydrogenated molecular NH₃BH₂NH₂BH₂NH₂BH₃ product. The mixed specimen was characterised by NMR and vibrational spectroscopies, and the cocrystal structure was analyzed from powder X-ray diffraction data supported by theoretical density functional theory calculations. The compound crystallises in a P2₁/c unit cell with the lattice parameters of a = 13.401(11) Å, b = 13.196(8) Å, c = 17.828(12) Å, β = 128.83(4)°, V = 2556(3) ų and Z = 16. Despite their impressive hydrogen content, similar to ammonia borane, both title compounds release hydrogen substantially polluted with borazine and traces of ammonia and diborane.