Braun Doris E
Institute of Pharmacy, University of Innsbruck, Innrain 52c, 6020 Innsbruck, Austria.
Phys Chem Chem Phys. 2019 Aug 21;21(31):17288-17305. doi: 10.1039/c9cp02572c. Epub 2019 Jul 26.
The monosolvate crystal energy landscapes of dapsone (DDS) including the solvents carbon tetrachloride, acetone, cyclohexanone, dimethyl formamide, tetrahydrofuran, methyl ethyl ketone, 1,2-dichloroethane, 1,4-dioxane, dichloromethane and chloroform were established using experimental and computational approaches. To rationalise and understand solvate formation, solvate stability and desolvation reactions a careful control of the experimental crystallisation and storage conditions, a range of thermoanalytical methods and crystal structure prediction were required. Six of the eight DDS monosolvates are reported and characterised for the first time. Structural similarity and diversity of the at ambient conditions unstable monosolvates were apparent from the computed crystal energy landscapes, which had the experimental packings as lowest energy structures. The computed structures were used as input for Rietveld refinements and isostructurality of four of the monosolvates was confirmed. Packing comparisons of the solvate structures and molecular properties of the solvent molecules indicated that both size/shape of the solvent molecule and the possible DDSsolvent interactions are the important factors for DDS solvate formation. Through the combination of experiment and theory solvate stability and structural features have been rationalised.
采用实验和计算方法建立了氨苯砜（DDS）与四氯化碳、丙酮、环己酮、二甲基甲酰胺、四氢呋喃、甲乙酮、1,2 -二氯乙烷、1,4 -二氧六环、二氯甲烷和氯仿等溶剂形成的单溶剂化物晶体能量景观。为了合理解释和理解溶剂化物的形成、溶剂化物稳定性和去溶剂化反应，需要仔细控制实验结晶和储存条件、一系列热分析方法以及晶体结构预测。首次报道并表征了八种DDS单溶剂化物中的六种。从计算得到的晶体能量景观中可以明显看出，在环境条件下不稳定的单溶剂化物的结构相似性和多样性，实验堆积结构为能量最低的结构。计算得到的结构用作Rietveld精修的输入，证实了四种单溶剂化物的同构性。溶剂化物结构的堆积比较以及溶剂分子的分子性质表明，溶剂分子的大小/形状和可能的DDS -溶剂相互作用都是DDS溶剂化物形成的重要因素。通过实验和理论相结合，对溶剂化物的稳定性和结构特征进行了合理解释。
