2,20-(Disulfanediyl)dibenzoic acid N,N-dimethylformamide monosolvate: Crystal structure, Hirshfeld surface analysis and computational study

The title 1:1 solvate, C14H10O4S2·C3H7NO, features a twisted molecule of 2,2'-dithiodibenzoic acid (DTBA), with the central C - S - S - C torsion angle being -88.57(6)°, and a molecule of dimethylformamide (DMF). The carboxylic acid groups are, respectively, close to co-planar and twisted with respect to the benzene rings to which they are connected as seen in the CO2/C6 torsion angles of 1.03(19) and 7.4(2)°. Intramolecular, hypervalent S?O interactions are noted [S?O = 2.6140(9) and 2.6827(9)Å]. In the crystal, four-molecule aggregates are formed via DTBA-O - H?O(DMF) and DTBA-O - H?O(DTBA) hydrogen bonding, the latter via an eight-membered {?OHCO}2 homosynthon. These are linked into supramolecular layers parallel to (011) via benzene-C - H?O(DTBA) and DTBA-C=O?p(benzene) interactions, with the connections between these, giving rise to a three-dimensional architecture, being of the type benzene-C - H?p(benzene). An analysis of the calculated Hirshfeld surfaces indicates, in addition to the aforementioned intermolecular contacts, the presence of stabilizing interactions between a benzene ring and a quasi-p-system defined by O - H?O hydrogen bonds between a DTBA dimer, i.e. the eight-membered {?OCOH}2 ring system, and between a benzene ring and a quasi-p(OCOH?OCH) system arising from the DTBA-O - H?O(DMF) hydrogen bond. The inter-centroid separations are 3.65 and 3.49Å, respectively.