Ternary and quaternary cocrystals of 2,7-dihydroxynaphthalene: systematic design with a large synthon module

Abstract

Ternary and quaternary cocrystals of 2,7-dihydroxynaphthalene are synthesized with N-bases and polyaromatic hydrocarbons.

Synthetic Strategies toward Higher Cocrystals of Some Resorcinols

“…As there were limited reports of DINAP cocrystals in the CSD, we crystallized DINAP with different N-donor bases to study the interactions and crystal packing. In this context, we mention the recent study of Mukherjee and Ahsan, who have reported the crystal structures of six ternaries, two ternary solvates, and two quaternary cocrystals of DINAP . We obtained 12 structures (6 binaries, 3 binary solvates, and 3 ternaries); a binary cocrystal reported by Brahma et al is also taken into consideration, and the following discussion pertains to all these 23 structures (6 + 2 + 2 + 12 + 1).…”

“…The former synthon, which we have earlier termed a MacGillivray synthon, contains two resorcinol molecules connected with a ditopic base, with the same base being found in both connections. An unusual closed synthon with two different ditopic bases was first observed by Paul et al The LSAM concept has also been invoked by Mukherjee and Ahsan in their recent study of ternary and quaternary cocrystal structures based on 2,7-dihydroxynapthalene (DINAP) …”

“…In this context, we mention the recent study of Mukherjee and Ahsan, who have reported the crystal structures of six ternaries, two ternary solvates, and two quaternary cocrystals of DINAP. 53 We obtained 12 structures (6 binaries, 3 binary solvates, and 3 ternaries); a binary cocrystal reported by Brahma et al 61 is also taken into consideration, and the following discussion pertains to all these 23 structures (6 + 2 + 2 + 12 + 1). Among the seven binaries, we observed the closed synthon in DINAP:TMP, the intercalated "Type A" synthon in DINAP:-PHEN, and the continuous "Type B" synthon in DI-NAM:DMQXN.…”

“…An unusual closed synthon with two different ditopic bases was first observed by Paul et al 52 The LSAM concept has also been invoked by Mukherjee and Ahsan in their recent study of ternary and quaternary cocrystal structures based on 2,7dihydroxynapthalene (DINAP). 53 The shape−size mimicry approach is a general one in crystal engineering and uses the fact that molecules of similar shapes and sizes can substitute for one another without major changes in the crystal structure; in many cases, these structures are isomorphous. Paul et al exploited the shape−size similarities of chloro, bromo, and methyl groups in substituted resorcinols to achieve five-and six-component solids, in which the fifth and sixth components are incorporated in a solid solution fashion at the site of the fourth component.…”

Structural Variability in Cocrystals: Occurrence of Variable Stoichiometry and High Z′ Forms in a Cocrystal System

“…This large synthon was observed before in the context of higher-order cocrystals. 42 The occurrence of this large synthon in solvated forms, however, indicates that these structures may require specific solvents. Forms X and XI are also formed by a similar large synthon (Figure 8c).…”