Solvent-induced polymorphism of three-dimensional hydrogen-bonded networks of hexakis(4-carbamoylphenyl)benzene
Solvent-induced polymorphism of three-dimensional hydrogen-bonded networks of hexakis(4-carbamoylphenyl)benzene
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DOI：
10.1021/ja0293103
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发表时间：
2003-03-12
影响因子：
15
通讯作者：
Yamaguchi, K
中科院分区：
文献类型：
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作者：
Kobayashi, K;Sato, A;Yamaguchi, K
确定了六（4-氨基苯基）苯(1)的三种三维（3-D）氢键网络的晶体结构，它们的网络形态在很大程度上取决于结晶条件。当该化合物从热DMSO中结晶时，得到的晶体1 -12DMSO（正交，Pca2(1)）通过1- d链作为6个伯胺基的氢键基序显示出3-D氢键多孔网络（a型）。A型网络创造了由6个1分子包围的腔室和沿着c轴的通道，在这里研究的1的网络多晶中具有最高的孔隙率。从n-PrOH和水的沸腾混合物中结晶得到1.6n-PrOH（单斜，P2(1)/c），通过环二聚体作为6个伯胺基的另一种氢键基序，表现出另一种3-D氢键多孔网络（B型）。B型网络沿a轴形成三角形通道，其横截面约为9.2 x 9.7 x 9.7埃（包括范德华半径）。的晶体结构。在水热条件下生成的H2O（单斜，P2(1)/c），显示出由螺旋链/环状二聚体/双聚体混合氢键基序组成的酰胺基（c型）无孔三维氢键网络链。溶剂诱导的3-D氢键网络1的拓扑异构源于(i)基于1的径向功能化六方结构的客体包合能力，（ii）宿主1中初级酰胺基团的顺质子和反质子的氢键供体能力与1和客体溶剂中氧原子的氢键受体能力之间的相关性，以及（iii）体结晶溶剂的极性。
The crystal structures for three types of three-dimensional (3-D) hydrogen-bonded networks of hexakis(4-carbamoylphenyl)benzene (1), the network morphologies of which depend greatly on crystallization conditions, have been determined. When this compound is crystallized from hot DMSO, the resulting crystals, 1 -12DMSO (orthorhombic, Pca2(1)), showed a 3-D hydrogen-bonded porous network (type A) via 1-D catemer chains as a hydrogen-bonding motif of six primary amide groups. The type A network creates chambers surrounded by six molecules of 1 and channels along the c axis to give the highest porosity among the network polymorphs of 1 investigated here. Crystallization from a boiling mixture of n-PrOH and water gave 1.6n-PrOH (monoclinic, P2(1)/c), which exhibits another type of 3-D hydrogen-bonded porous network (type B) via cyclic dimers as another hydrogen-bonding motif of six primary amide groups. The type B network leads to triangle-like channels along the a axis having a cross section of ca. 9.2 x 9.7 x 9.7 Angstrom (including van der Waals radii). The crystal structure of 1.H2O (monoclinic, P2(1)/c), which was produced under hydrothermal conditions, showed a nonporous 3-D hydrogen-bonded network chain of amide groups (type C) composed of a mixed hydrogen bonding motif of helical catemer chains/cyclic dimer/catemer. Solvent-induced topological isomerism of these 3-D hydrogen-bonded networks of 1 arises from (i) the guest inclusion ability based on a radially functionalized hexagonal structure of 1, (ii) the correlation between the hydrogen bond donor ability of the syn and anti protons of the primary amide group in host 1 and the hydrogen bond acceptor ability of the oxygen atoms of 1 and guest solvents, and (iii) the polarity of the bulk crystallization solvents.