Characteristic Hydrogen Bonding Observed in the Crystals of Aromatic Sulfonamides: 1D Chain Assembly of Molecules and Chiral Discrimination on Crystallization
Characteristic Hydrogen Bonding Observed in the Crystals of Aromatic Sulfonamides: 1D Chain Assembly of Molecules and Chiral Discrimination on Crystallization
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DOI：
10.1021/acs.cgd.9b00159
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发表时间：
2019-05-01
影响因子：
3.8
通讯作者：
Azumaya, Isao
中科院分区：
文献类型：
--
作者：
Kikkawa, Shoko;Masu, Hyuma;Azumaya, Isao
N-苯基苯磺酰胺优先以（+）-或（-）-向斜构象存在，其将芳环在两端以相同的方向扭转。我们系统地分析了苯环上带有甲基、乙基和/或甲氧基的仲芳磺酰胺的晶体结构。在85个晶体中的81个中观察到磺酰胺质子和磺酰氧之间的分子间氢键。分子间氢键模式可分为四种类型，即二聚体，锯齿形，螺旋形和直模式，保留了磺胺部分的向斜构象。我们研究了氢键模式和显示手性结晶的化合物的比例之间的关系。在我们对芳族磺酰胺分子间氢键进行分类的基础上，除了Kryptoracemates外，具有对映体向斜构象的二聚体和锯齿形图案的晶体本质上成为非手性的。相反，在晶体中具有螺旋或直图案的化合物的高比例显示手性结晶。我们的分类是有用的讨论关于分子组装体的手性，在晶体中的分子的构象手性的基础上。
N-Phenylbenzenesulfonamides exist preferentially in (+)-or (-)-synclinal conformations, which place the aromatic rings at both ends in the same direction with a twist. We have systematically analyzed the crystal structure of secondary aromatic sulfonamides bearing methyl, ethyl, and/or methoxy groups on the benzene rings. Intermolecular hydrogen bonding between the sulfonamide protons and sulfonyl oxygens was observed in 81 out of 85 crystals. The intermolecular hydrogen-bonding patterns could be classified into four types, i.e. Dimeric, Zigzag, Helical, and Straight patterns, with retention of the synclinal conformation of the sulfonamide moiety. We investigated the relationship between the hydrogen-bonding pattern and the proportion of the compounds that show chiral crystallization. On the basis of our classification of the intermolecular hydrogen bonds of aromatic sulfonamides, the crystals with Dimeric and Zigzag patterns, which both have enantiomeric synclinal conformers, intrinsically become achiral, except for kryptoracemates. In contrast, a high proportion of compounds with Helical or Straight patterns in the crystals showed chiral crystallization. Our classification is useful for discussion regarding the chirality of molecular assemblies, on the basis of the conformational chirality of the molecules in the crystal.