Potential of polyfluoroaromatic compounds containing OH, COOH, and mixed H-donor functions as co-formers in co-crystallization with 18-crown-6 ether was explored. Pentafluorophenol, 1,3- and 1,4-dihydroxytetrafluorobenzenes and pentafluorobenzoic acid form with 18-crown-6 hydrated co-crystals containing one water molecule per H-donor group upon contact of the solutions with atmospheric moisture; pentafluorophenol gives a co-crystal with double the amount of water in aqueous EtOH. Aminotetrafluorobenzyl alcohol and aminotetrafluorobenzoic acid are capable of forming anhydrous 1:1 and 2:1 co-crystals with 18-crown-6. In the crystalline hydrates, co-formers molecules are connected via water-mediated synthon [C(O)]OH⋯O(H)H⋯O_cr. According to quantum chemical calculations, the participation of each water linker molecule in H-bonding increases the stability of the supramolecular structure by about 100 kJ mol⁻¹. Associates of bifunctional arenes exhibit H-bonded 1D assembly as an only structure-determining motif; molecules of monofunctional arenes in the co-crystals are bound via π_F⋯π_F stacking to give the H-bonded/π-stacked 1D assembly. The calculated π-stacking energy depends on the nature of the H-donor function (NH₂, OH, COOH), decreasing with a decrease in the molecule dipole moment.

探索了含有OH，COOH和混合的H-供体的多氟芳族化合物在与18-冠-6醚共结晶中作为共形成剂的潜力。当溶液与大气中的水分接触时，五氟苯酚，1,3-和1,4-二羟基四氟苯与五氟苯甲酸与18个皇冠6个水合共晶体形成一个水分子，每个H供体基团含有一个水分子。五氟苯酚产生的共晶体与在EtOH水溶液中的水量加倍。氨基四氟苄醇和氨基四氟苯甲酸能够与18-crown-6形成无水1：1和2：1共结晶。在结晶水合物中，共形成物分子通过水介导的合成子[C（O）] O H⋯O（H）H⋯O _cr连接。根据量子化学计算，每个水连接分子参与H键合将超分子结构的稳定性提高约100kJ mol ^-1。双官能团的缔合体表现出H键合的1D组装作为唯一的结构决定基元。在共晶的单官能芳烃的分子通过结合π _˚F ⋯π _˚F堆叠，得到H-粘结/π堆叠1D组件。计算出的π-堆积能取决于H-给体功能（NH ₂，OH，COOH）的性质，随着分子偶极矩的减小而减小。