Hydrogen Bond Donor/Acceptor Ratios of the Coformers: Do They Really Matter for the Prediction of Molecular Packing in Cocrystals? the Case of Benzamide Derivatives with Dicarboxylic Acids

Seven new 4-aminobenzamide cocrystals/salts with dicarboxylic acids and one 4-hydroxybenzamide/malonic acid 1:1 cocrystal have been obtained and characterized. Analysis of the Cambridge Structural Database of para-substituted benzamide derivatives cocrystals with dicarboxylic acids has been carried out to understand the influence of hydrogen bond donor/acceptor ratios of the coformers on molecular packing similarity in cocrystals. The concept of supramolecular constructs has been used to compare 37 benzamide derivatives cocrystals/salts. Common zero- to three-dimensional structure fragments have been identified and discussed. Two types of zero-dimensional and two types of one-dimensional fragments of closely para-substituted benzamide derivatives have been identified as the dominating motifs. It has been identified that a deviation from the ratio of hydrogen bond donors and acceptors in cocrystal formers increases the probability of formation of multicomponent crystal solvates. In a number of groups of si...