Crystal structure of a new monoclinic polymorph of 2,4-di­hydroxy­benzaldehyde 4-methyl­thio­semi­carbazone

The title compound, C(9)H(11)N(3)O(2)S, is a second monoclinic (P2(1)/c) polymorph of the previously reported Cc form [Tan et al. (2008b ▸). Acta Cryst. E64, o2224]. The mol­ecule is non-planar, with the dihedral angle between the N(3)CS residue (r.m.s. deviation = 0.0816 Å) and the benzene ring being 21.36 (4)°. The conformation about the C=N bond [1.292 (2) Å] is E, the two N-bound H atoms are anti, and the inner hy­droxy O-bound and outer amide N-bound H atoms form intra­molecular hydrogen bonds to the imine N atom. Crucially, the H atom of the outer hy­droxy group is approximately syn to the H atom of the benzene C atom connecting the two C atoms bearing the hy­droxy substituents. This arrangement enables the formation of supra­molecular tubes aligned along [010] and sustained by N—H⋯O, O—H⋯S and N—H⋯S hydrogen bonds; the tubes pack with no specific inter­actions between them. While the mol­ecular structure in the Cc form is comparable, the H atom of the outer hy­droxy group is approximately anti, rather than syn. This different orientation leads to the formation a three-dimensional architecture based on N—H⋯O and O—H⋯S hydrogen bonds.