Expected and unexpected products of reactions of 2-hydrazinylbenzo­thia­zole with 3-nitro­benzene­sulfonyl chloride in different solvents

The syntheses and crystal structures of 2-[2-(propan-2-yl­idene)hydrazin­yl]-1,3-benzo­thia­zol-3-ium 3-nitro­benzene­sulfonate (C(10)H(12)N(2)S(+)·C(6)H(4)NO(5)S(−)), (I), 2-[2-(3-nitro­benzene­sulfon­yl)hydrazin­yl]-1,3-benzo­thia­zole (C(13)H(10)N(4)O(4)S(2)), (II) and 2-[2-(3-nitro­benzene­sulfon­yl)hydrazin­yl]-1,3-benzo­thia­zol-3-ium 3-nitro­benzene­sulfonate (C(13)H(11)N(4)O(4)S(2) (+)·C(6)H(4)NO(5)S(−)), (III) are reported. Salt (I) arose from an unexpected reaction of 2-hydrazinylbenzo­thia­zole with the acetone solvent in the presence of 3-nitro­benzene­sulfonyl chloride, whereas (II) and (III) were recovered from the equivalent reaction carried out in methanol. The crystal of (I) features ion pairs linked by pairs of N—H⋯O(s) (s = sulfonate) hydrogen bonds; adjacent cations inter­act by way of short π–π stacking inter­actions between the thia­zole rings [centroid–centroid separation = 3.4274 (18) Å]. In (II), which crystallizes with two neutral mol­ecules in the asymmetric unit, the mol­ecules are linked by N—H⋯N and N—H⋯O(n) (n = nitro) hydrogen bonds to generate [[Image: see text]1[Image: see text]] chains, which are cross-linked by C—H⋯O and π–π stacking inter­actions. The crystal of (III) features centrosymmetric tetra­mers (two cations and two anions) linked by cooperative N—H⋯O hydrogen bonds; C—H⋯O and π–π inter­actions occur between tetra­mers.