Abstract
The asymmetric unit of the three-component title compound, 2,2'-di-thiodi-benzoic acid-2-chloro-benzoic acid-N,N-di-methyl-formamide (1/1/1), C14H10O4S2·C7H5ClO2·C3H7NO, contains a mol-ecule each of 2,2'-di-thiodi-benzoic acid (DTBA), 2-chloro-benzoic acid (2CBA) and di-methyl-formamide (DMF). The DTBA mol-ecule is twisted [the C-S-S-C torsion angle is 88.37 (17)°] and each carb-oxy-lic group is slightly twisted from the benzene ring to which it is connected [CO2/C6 dihedral angles = 7.6 (3) and 12.5 (3)°]. A small twist is evident in the mol-ecule of 2CBA [CO2/C6 dihedral angle = 4.4 (4)°]. In the crystal, the three mol-ecules are connected by hydrogen bonds with the two carb-oxy-lic acid residues derived from DTBA and 2CBA forming a non-symmetric eight-membered {⋯HOCO}2 synthon, and the second carb-oxy-lic acid of DTBA linked to the DMF mol-ecule via a seven-membered {⋯HOCO⋯HCO} heterosynthon. The three-mol-ecule aggregates are connected into a supra-molecular chain along the a axis via DTBA-C-H⋯O(hydroxyl-2CBA), 2CBA-C-H⋯O(hydroxyl-DTBA) and DTBA-C-H⋯S(DTBA) inter-actions. Supra-molecular layers in the ab plane are formed as the chains are linked via DMF-C-H⋯S(DTBA) contacts, and these inter-digitate along the c-axis direction without specific points of contact between them. A Hirshfeld surface analysis points to additional but, weak contacts to stabilize the three-dimensional architecture: DTBA-C=O⋯H(phenyl-DTBA), 2CBA-Cl⋯H(phenyl-DTBA), as well as a π-π contact between the delocalized eight-membered {⋯HOC=O}2 carb-oxy-lic dimer and the phenyl ring of 2CBA. The latter was confirmed by electrostatic potential (ESP) mapping.
Highlights
A 1:1:1 co-crystal solvate comprising 2,20-dithiodibenzoic acid, 2-chlorobenzoic acid and N,N-dimethylformamide: crystal structure, Hirshfeld surface analysis and computational study
The dithiodibenzoic acid (DTBA) molecule is twisted [the C—S—S—C torsion angle is 88.37 (17)] and each carboxylic group is slightly twisted from the benzene ring to which it is connected [CO2/C6 dihedral angles = 7.6 (3) and 12.5 (3)]
The three-molecule aggregates are connected into a supramolecular chain along the a axis via DTBA-C— HÁ Á ÁO(hydroxyl-2-chlorobenzoic acid (2CBA)), 2CBA-C—HÁ Á ÁO(hydroxyl-DTBA) and DTBA-C— HÁ Á ÁS(DTBA) interactions
Summary
Recent bibliographic reviews have highlighted the rich coordination chemistry based on ligands derived from 2-mercaptobenzoic acid (2-MBA) (Wehr-Candler & Henderson, 2016) and its 3- and 4-isomeric analogues (Tiekink & Henderson, 2017). One reason for the scarcity of cocrystals containing 2-MBA is the propensity for the acid to be oxidized, to generate DTBA, during co-crystallization experiments with bipyridyl-type molecules (Broker & Tiekink, 2007) and with other carboxylic acids (Tan & Tiekink, 2019a). While the anticipated coformer DTBA was observed after the co-crystallization of 2-MBA with 2-chlorobenzoic acid (2CBA), and recrystallization from a toluene/dimethylformamide solution (50:50 v/v), a solvent dimethylformamide molecule was found in the resultant co-crystal solvate. In this threecomponent crystal, one of the carboxylic acid groups of the DTBA molecule forms hydrogen bonds to DMF rather than to 2CBA. Co-planarity is noted between the chloride atom and benzene ring plane with the r.m.s deviation from the least-squares plane through the seven non-hydrogen atoms being 0.027 A
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