4-[(1E)-({[Benzylsulfanyl)methanethioyl]amino}-imino)methyl] benzene-1,3-diol chloroform hemisolvate: crystal structure, Hirshfeld surface analysis and computational study

The title hydrazine carbodithioate chloroform hemisolvate, 2C(15)H(14)N(2)O(2)S(2)center dot-CHCl3, comprises two independent hydrazine carbodithioate molecules, A and B, and a chloroform molecule; the latter is statistically disordered about its molecular threefold axis. The common features of the organic molecules include an almost planar, central CN2S2 chromophore [r.m.s. deviation = 0.0203 angstrom (A) and 0.0080 angstrom (B)], an E configuration about the imine bond and an intramolecular hydroxyl-O-H center dot center dot center dot N(imine) hydrogen bond. The major conformational difference between the molecules 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)degrees (A) and 54.73 (7)degrees (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 molecule is planar with the exception of the perpendicular phenyl ring. In the molecular packing, the A and B molecules assemble into a two-molecule aggregate via N-H center dot center dot center dot S hydrogen bonds and eight-membered {center dot center dot center dot HNCS}(2) synthons. The dimeric assemblies are connected into supramolecular chains via hydroxyl-O-H center dot center dot center dot-O(hydroxyl) hydrogen bonds and these are linked into a double-chain through hydroxy-O-H center dot center dot center dot-pi(phenyl) interactions. The double-chains are connected into a three-dimensional architecture through phenyl-C-H center dot center dot center dot-O(hydroxyl) and phenyl-C-H center dot center dot center dot-pi(phenyl) interactions. The overall assembly defines columns along the a-axis direction in which reside the chloroform molecules, which are stabilized by chloroform-methine-C- H center dot center dot center dot S(thione) and phenyl-C-H center dot center dot center dot Cl contacts. The analysis of the calculated Hirshfeld surfaces, non-covalent interaction plots and interaction energies confirm the importance of the above-mentioned interactions, but also of cooperative, non-standard interactions such as pi(benzene)center dot center dot center dot-pi(hydrogen-bond-mediated-ring) contacts.