Domasevitch Kostiantyn V, Ponomarova Vira V
Inorganic Chemistry Department, National Taras Shevchenko University of Kyiv, Volodymyrska Str. 64/13, 01601 Kyiv, Ukraine.
Acta Crystallogr E Crystallogr Commun. 2021 Oct 13;77(Pt 11):1109-1115. doi: 10.1107/S2056989021010227. eCollection 2021 Nov 1.
In the structures of the title salts, poly[[μ-4-(3,5-di-nitro-pyrazol-4-yl)-3,5-di-nitro-pyrazol-1-ido]rubidium], [Rb(CHNO)] , (), and its isostructural caesium analogue [Cs(CHNO) , (), two independent cations 1 and 2 ( = Rb, Cs) are situated on a crystallographic twofold axis and on a center of inversion, respectively. Mutual inter-molecular hydrogen bonding between the conjugate 3,5-dinito-pyrazole NH-donor and 3,5-di-nitro-pyrazole N-acceptor sites of the anions [N⋯N = 2.785 (2) Å for () and 2.832 (3) Å for ()] governs the self-assembly of the translation-related anions in a predictable fashion. Such one-component modular construction of the organic subtopology supports the utility of the crystal-engineering approach towards designing the structures of polynitro energetic materials. The anionic chains are further linked by multiple ion-dipole inter-actions involving the 12-coordinate cations bonded to two pyrazole N-atoms [Rb-N = 3.1285 (16), 3.2261 (16) Å; Cs-N = 3.369 (2), 3.401 (2) Å] and all of the eight nitro O-atoms [Rb-O = 2.8543 (15)-3.6985 (16) Å; Cs-O = 3.071 (2)-3.811 (2) Å]. The resulting ionic networks follow the CsCl topological archetype, with either metal or organic ions residing in an environment of eight counter-ions. Weak lone pair-π-hole inter-actions [pyrazole-N atoms to NO groups; N⋯N = 2.990 (3)-3.198 (3) Å] are also relevant to the packing. The Hirshfeld surfaces and percentage two-dimensional fingerprint plots for () and () are described.
在标题盐的结构中，聚[[μ-4-(3,5-二硝基-吡唑-4-基)-3,5-二硝基-吡唑-1-铟]铷]，[Rb(CHNO)] ，()，及其同构铯类似物[Cs(CHNO) ，()，两个独立的阳离子1和2（= Rb，Cs）分别位于晶体学二重轴和对称中心上。阴离子的共轭3,5-二硝基-吡唑NH供体位点与3,5-二硝基-吡唑N受体位点之间的分子间氢键相互作用[N⋯N = ()为2.785 (2) Å，()为2.832 (3) Å]以可预测的方式控制平移相关阴离子的自组装。有机子拓扑的这种单组分模块化结构支持了晶体工程方法在设计多硝基含能材料结构方面的实用性。阴离子链通过涉及与两个吡唑N原子键合的12配位阳离子的多个离子 - 偶极相互作用进一步连接[Rb - N = 3.1285 (16)，3.2261 (16) Å；Cs - N = 3.369 (2)，3.401 (2) Å]以及所有八个硝基O原子[Rb - O = 2.8543 (15) - 3.6985 (16) Å；Cs - O = 3.071 (2) - 3.811 (2) Å]。所得的离子网络遵循CsCl拓扑原型，金属离子或有机离子位于八个反离子的环境中。弱孤对 - π孔相互作用[吡唑 - N原子与NO基团；N⋯N = 2.990 (3) - 3.198 (3) Å]也与堆积有关。描述了()和()的Hirshfeld表面和二维指纹图谱百分比。
