2,2'-(Disulfanedi-yl)di-benzoic acid N,N-di-methyl-formamide monosolvate: crystal structure, Hirshfeld surface analysis and computational study.

Sang Loon Tan,Edward R T Tiekink

doi:10.1107/s2056989020008257

Sang Loon Tan, Edward R T Tiekink

Open Access

https://doi.org/10.1107/s2056989020008257

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Abstract

The title 1:1 solvate, C14H10O4S2·C3H7NO, features a twisted mol-ecule of 2,2'-di-thiodi-benzoic acid (DTBA), with the central C-S-S-C torsion angle being -88.57 (6)°, and a mol-ecule of di-methyl-formamide (DMF). The carb-oxy-lic 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)°. Intra-molecular, hypervalent S←O inter-actions are noted [S⋯O = 2.6140 (9) and 2.6827 (9) Å]. In the crystal, four-mol-ecule 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 supra-molecular layers parallel to (011) via benzene-C-H⋯O(DTBA) and DTBA-C=O⋯π(benzene) inter-actions, with the connections between these, giving rise to a three-dimensional architecture, being of the type benzene-C-H⋯π(benzene). An analysis of the calculated Hirshfeld surfaces indicates, in addition to the aforementioned inter-molecular contacts, the presence of stabilizing inter-actions between a benzene ring and a quasi-π-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-π(OCOH⋯OCH) system arising from the DTBA-O-H⋯O(DMF) hydrogen bond. The inter-centroid separations are 3.65 and 3.49 Å, respectively.

Highlights

The title 1:1 solvate, C14H10O4S2ÁC3H7NO, features a twisted molecule of 2,20dithiodibenzoic acid (DTBA), with the central C—S—S—C torsion angle being À88.57 (6), and a molecule of dimethylformamide (DMF)
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--system defined by O—HÁ Á ÁO hydrogen bonds between a DTBA dimer, i.e. the eight-membered {Á Á ÁOCOH}2 ring system, and between a benzene ring and a quasi-(OCOHÁ Á ÁOCH) system arising from the DTBA-O—HÁ Á ÁO(DMF) hydrogen bond
Co-crystal formation with 2-mercaptobenzoic acid (2-MBA) is fraught as during crystallization, this is usually oxidized to 2,20-dithiodibenzoic acid (DTBA) (Broker & Tiekink, 2007; Broker et al, 2008)

Summary

Chemical context

Co-crystal formation with 2-mercaptobenzoic acid (2-MBA) is fraught as during crystallization, this is usually oxidized to 2,20-dithiodibenzoic acid (DTBA) (Broker & Tiekink, 2007; Broker et al, 2008). It was found the anticipated {Á Á ÁHOCO}2 synthon was not always formed but was usurped by a DTBA-O— HÁ Á ÁO(DMF) hydrogen bond for one of the carboxylic acids, i.e. in the 1:1:1 co-crystal solvate DTBA:2-ClBA:DMF (Tan & Tiekink, 2019d); DMF is dimethylformamide. The crystals were obtained from the recrystallization of 2-mercaptobenzoic acid from a benzene/ DMF (5 ml/1 ml v/v) solution indicating the acid oxidized to DTBA during crystallization. Intramolecular hypervalent S O interactions (Nakanishi et al, 2007) are indicated as the carbonyl-O2 and O4 atoms are orientated towards the disulfide-S1 and S2 atoms, respectively, with the S1Á Á ÁO2 and S2Á Á ÁO4 separations being 2.6140 (9) and 2.6827 (9) A , respectively

Supramolecular features

Hirshfeld surface analysis

Computational chemistry

Database survey

Synthesis and crystallization

Refinement