The crystal structures of two polymorphs of a phenazine hexacyanoferrate(II) salt/cocrystal, with the formula (Hphen)₃[H₂Fe(CN)₆][H₃Fe(CN)₆]·2(phen)·2H₂O, are reported. The polymorphs are comprised of (Hphen)₂[H₂Fe(CN)₆] trimers and (Hphen)[(phen)₂(H₂O)₂][H₃Fe(CN)₆] hexamers connected into two‐dimensional (2D) hydrogen‐bonded networks through strong hydrogen bonds between the [H₂Fe(CN)₆]²⁻ and [H₃Fe(CN)₆]⁻ anions. The layers are further connected by hydrogen bonds, as well as through π–π stacking of phenazine moieties. Aside from the identical 2D hydrogen‐bonded networks, the two polymorphs share phenazine stacks comprising both protonated and neutral phenazine molecules. On the other hand, the polymorphs differ in the conformation, placement and orientation of the hydrogen‐bonded trimers and hexamers within the hydrogen‐bonded networks, which leads to different packing of the hydrogen‐bonded layers, as well as to different hydrogen bonding between the layers. Thus, aside from an exceptional number of symmetry‐independent units (nine in total), these two polymorphs show how robust structural motifs, such as charge‐assisted hydrogen bonding or π‐stacking, allow for different arrangements of the supramolecular units, resulting in polymorphism.

中文翻译：

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吩嗪六氰合铁酸盐（II）水合物的多晶型物：二维氢键网络中的超分子异构

式（Hphen）₃ [H ₂ Fe（CN）₆ ] [H ₃ Fe（CN）₆ ]·2（phen）·2H ₂的吩嗪六氰合铁酸盐（II）盐/共晶体的两个多晶型物的晶体结构O，正在报告。多晶型物由（Hphen）₂ [H ₂ Fe（CN）₆ ]三聚体和（Hphen）[（phen）₂（H ₂ O）₂ ] [H ₃ Fe（CN）₆ ]六聚体连接成二维（2D）通过[H ₂ Fe（CN）₆ ] ²⁻和[H₃ Fe（CN）₆ ] ^-阴离子。各层通过氢键以及吩嗪部分的π-π堆积进一步连接。除了相同的2D氢键网络外，这两种多晶型物还共享包含质子化和中性吩嗪分子的吩嗪叠层。另一方面，多晶型物在氢键网络中氢键三聚体和六聚体的构象，位置和取向不同，这导致氢键层的堆积不同，以及氢键层之间的氢键不同。层。因此，除了数量众多的对称独立单元（总共九个）以外，这两个多晶型物还显示出稳健的结构基序（例如电荷辅助氢键或π堆积）如何允许超分子单元的不同排列，从而导致多态性。