Achiral Benzoic Acid Derivatives as Chiral Cocrystal Building Blocks in Supramolecular Chemistry: Adducts with Organic Amines

Achiral benzoic acid derivatives were cocrystallized with a range of amines, affording binary or ternary cocrystals
[(p-nitrobenzoic acid)·(2-aminopyridine)] (1), [(p-nitrobenzoic acid)·(4,4‘-bipyridine)] (2), [(p-nitrobenzoic acid)·(p-methoxyaniline)]
(3), [(3,5-dinitrobenzoic acid)·(2,2‘-bipyridine)] (4), [(3,5-dinitrobenzoic acid)·(4, 4‘-bipyridine)] (5), and [(phthalic acid)·(2-aminobenzimidazole)] (6) under specified conditions. All the prepared cocrystals have a common structural feature of the 21 screw
axis. It is noteworthy that the cocrystals 1*, 4*, and 6*, achiral benzoic acid derivatives and nitrogen bases, are noncentrosymmetric
and chiral cocrystals. Strong N−H···O interactions are involved in the chiral cocrystals, undoubtedly following the best donor/acceptor guidelines. X-ray single-crystal diffraction studies reveal that the stronger N−H···O and O−H···N interactions, as well as
weaker C−H···O ones, are all among the driving forces for the construction of the hydrogen-bonding networks in 1−6. Thus, a
two-dimensional (2D) framework is constructed for 2, and a three-dimensional (3D) column framework is constructed for 3 by
multiple hydrogen bonds. There are pairwise interwoven sheets in 4 and 6. For 5, a V-shaped arrangement of molecules exhibits a
parallel orientation.

非手性苯甲酸衍生物与一系列胺类化合物共结晶，获得了二元或三元共结晶。具体包括[(对-硝基苯甲酸)·(2-氨基吡啶)]（1）、[(对-硝基苯甲酸)·(4,4'-双吡啶)]（2）、[(对-硝基苯甲酸)·(对-甲氧基苯胺)]（3）、[(3,5-二硝基苯甲酸)·(2,2'-双吡啶)]（4）、[(3,5-二硝基苯甲酸)·(4, 4'-双吡啶)]（5）以及[(邻苯二甲酸)·(2-氨基苯并咪唑)]（6），均是在特定条件下制备的。所有制备的共结晶均具有21螺旋轴的共有结构特征。值得注意的是，共结晶1*、4*和6*，即非手性苯甲酸衍生物与氮碱，均是非中心对称且手性的。手性共结晶中涉及强烈的N−H···O氢键作用，无疑遵循了最佳的供体/受体准则。X射线单晶衍射研究表明，更强的N−H···O和O−H···N氢键作用，以及较弱的C−H···O氢键作用，均为构建1−6中氢键网络的驱动力。因此，2构建了一个二维（2D）框架，而3则通过多重氢键构建了一个三维（3D）柱状框架。4和6中存在相互交织的薄片。对于5，分子的V形排列表现出平行取向。