Packing Polymorphism on the Example of 5-Hydroxy-1-(4-Methylbenzyl)-3-Chloro-4-[(4-Chlorophenyl)Sulfanyl]-1,5-Dihydro-2H-Pyrrol-2-One: A Crystallographic, Thermochemical, and Spectroscopic Study

Homochiral versus Heterochiral Crystallization of 3-Pyrrolin-2-one Thioether Results in the Score 2:1 in Favor of Homochirality

“…The energy diagram allows one to characterize the phase behavior and the relationship between the phases in detail. Therefore, we plotted the diagram (Figure ) based on experimental data and some assumptions by the known algorithm. ,, Namely, it was possible to estimate the unknown melting temperatures of the enantiopure monoclinic and hexagonal phases as the points of intersection of the lines of crystal phases with the energy level of the enantiopure melt. Because the mixture of melts of individual stereoisomers is well described by the ideal solution model, the corresponding line (cyan one in Figure ) should lie above the line of the racemic melt (light green) by the value of the entropy of mixing of liquid enantiomers, that is, RT ln 2.…”

“…At the same time, in the crystal of monoclinic 6c , the main supramolecular associate is a heterochiral chain along the glide plane (Figure d). Among previously studied racemic compounds of pyrrolin-2-one thioethers, − which are usually arranged by 0D centrosymmetric heterochiral H-bonded dimers, crystal 6c is the first repetitive showing a 1D heterochiral chain.…”

“…They exhibit identical heterochiral hydrogen-bonded cyclic dimers as a main supramolecular motif. 17 Classical hydrogen bonds combined with Cl•••O interactions lead to 1D chains. The main structural difference relates to the combining of these chains in 2D layers with a "parallel" mode in the triclinic modification and a "herringbone" mode in the monoclinic one.…”

“…For rac -3-chloro-4-[(4-chlorophenyl)­sulfanyl]-5-hydroxy-1-(4-methylbenzyl)-1,5-dihydro-2 H -pyrrol-2-one ( 2 ), two packing polymorphic racemic compounds were observed. They exhibit identical heterochiral hydrogen-bonded cyclic dimers as a main supramolecular motif . Classical hydrogen bonds combined with Cl···O interactions lead to 1D chains.…”

Solubility- and melting-based approaches to evaluate the inner-crystal enantiophobia and enantiophilia undergoing a structural change within a homologous series, exemplified by chiral glycerol ethers

“…The methodology described was originally suggested by us 26 and has since been employed in other prior studies. 14,35,[49][50][51] Here, we will provide a detailed and improved step-by-step description of the calculations essential for constructing an energy diagram.…”