4-[(1E)-({[(Benzyl-sulfan-yl)methane-thio-yl]amino}-imino)-meth-yl]benzene-1,3-diol chloro-form hemisolvate: crystal structure, Hirshfeld surface analysis and computational study

The title hydrazine carbodi-thio-ate chloro-form hemisolvate, 2C15H14N2O2S2·CHCl3, comprises two independent hydrazine carbodi-thio-ate mol-ecules, A and B, and a chloro-form mol-ecule; the latter is statistically disordered about its mol-ecular threefold axis. The common features of the organic mol-ecules include an almost planar, central CN2S2 chromophore [r.m.s. deviation = 0.0203 Å (A) and 0.0080 Å (B)], an E configuration about the imine bond and an intra-molecular hydroxyl-O-H⋯N(imine) hydrogen bond. The major conformational difference between the mol-ecules is seen in the relative dispositions of the phenyl rings as indicated by the values of the dihedral angles between the central plane and phenyl ring of 71.21 (6)° (A) and 54.73 (7)° (B). Finally, a difference is seen in the disposition of the outer hydroxyl-H atoms, having opposite relative orientations. In the calculated gas-phase structure, the entire mol-ecule is planar with the exception of the perpendicular phenyl ring. In the mol-ecular packing, the A and B mol-ecules assemble into a two-mol-ecule aggregate via N-H⋯S hydrogen bonds and eight-membered {⋯HNCS}2 synthons. The dimeric assemblies are connected into supra-molecular chains via hydroxyl-O-H⋯O(hydrox-yl) hydrogen bonds and these are linked into a double-chain through hy-droxy-O-H⋯π(phen-yl) inter-actions. The double-chains are connected into a three-dimensional architecture through phenyl-C-H⋯O(hydrox-yl) and phenyl-C-H⋯π(phen-yl) inter-actions. The overall assembly defines columns along the a-axis direction in which reside the chloro-form mol-ecules, which are stabilized by chloro-form-methine-C-H⋯S(thione) and phenyl-C-H⋯Cl contacts. The analysis of the calculated Hirshfeld surfaces, non-covalent inter-action plots and inter-action energies confirm the importance of the above-mentioned inter-actions, but also of cooperative, non-standard inter-actions such as π(benzene)⋯π(hydrogen-bond-mediated-ring) contacts.