Two new tetrahydrazinium dihalide dodecahydro-closo-dodecaborates (N₂H₅)₄X₂[B₁₂H₁₂] (X^– = Cl^– and Br^–) were successfully synthesized via the direct reaction of dihydrazinium dodecahydro-closo-dodecaborate (N₂H₄)₂[B₁₂H₁₂] with hydrazinium halides (N₂H₅)Cl and (N₂H₅)Br in aqueous media. The resulting isotypic compounds crystallize monoclinically in the space group P2₁/c with similar unit-cell parameters (a = 681.98(4) pm, b = 1025.38(6) pm, c = 1325.38(8) pm, and β = 98.393(3)° for the chloride and a = 686.05(4) pm, b = 1032.51(6) pm, c = 1316.04(8), and β = 97.449(3)° for the bromide). Their crystal structure was elucidated using single-crystal X-ray diffraction techniques, unveiling a new unique arrangement for the composition A₄B₂C (A = hydrazinium, B = halide, and C = dodecahydro-closo-dodecaborate). This distinctive structural configuration sets it apart from compounds exhibiting other A₄B₂C arrangements, such as the spinel or double-perovskite structure type. In this new structure, the halide anions are coordinated by five hydrazinium cations, creating triangular bipyramidal polyhedra. These are interconnected via edge- and corner-sharing, resulting in the formation of hexagonal tunnels along the [100] direction. Within each of these tunnels, the [B₁₂H₁₂]^2– clusters reside centrally located. Differential scanning calorimetry analyses demonstrate that these compounds contain a substantial amount of energy that is released during their thermal decomposition.

中文翻译：

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具有新型六边形 A4B2C 隧道结构的新型含能十二氢-氯十二硼酸盐 （N2H5）4X2[B12H12] （X = Cl 和 Br）


通过十二氢氯藻-氯索-十二硼酸盐 （N₂H₄）₂[B₁₂H₁₂] 与卤化物肼 （N₂H₅）Cl 的直接反应，成功合成了两种新的十二氢氯唑-十二硼酸盐四肼-十二氢-氯唑-十二硼酸盐 （N₂H₅）₄X₂[B₁₂H₁₂] （X^– = Cl^– 和 Br^–）和 （N₂H₅）Br 在水性介质中。所得的同型化合物在空间群 P2₁/c 中单临床结晶，具有相似的晶胞参数（a = 681.98（4） pm，b = 1025.38（6） pm，c = 1325.38（8） pm，氯化物 β = 98.393（3）°，a = 686.05（4） pm，b = 1032.51（6） pm，c= 1316.04（8），溴化物的 β = 97.449（3）°）。使用单晶 X 射线衍射技术阐明了它们的晶体结构，揭示了成分 A₄B₂C（A = 肼，B = 卤化物，C = 十二氢-氯唑-十二硼酸盐）的新独特排列。这种独特的结构配置使其有别于表现出其他 A₄B₂C 排列的化合物，例如尖晶石或双钙钛矿结构类型。在这种新结构中，卤化物阴离子由五个肼阳离子配位，形成三角形双锥多面体。它们通过边和角共享相互连接，从而沿 [100] 方向形成六边形隧道。 在每条隧道中，[B₁₂H₁₂]^2– 星团位于中心位置。差示扫描量热分析表明，这些化合物在热分解过程中含有大量释放的能量。