The crystal structures of six halobismuth(III) salts of variously substituted aminopyridinium cations display discrete mononuclear [BiCl₆]³⁻ and dinuclear [Bi₂X₁₀]⁴⁻ anions (X = Cl or Br), and polymeric cis‐double‐halo‐bridged [Bi_nX_4n]ⁿ⁻ anionic chains (X = Br or I). Bis(2‐amino‐3‐ammoniopyridinium) hexachloridobismuth(III) chloride monohydrate, (C₅H₉N₃)₂[BiCl₆]Cl·H₂O, (1), contains discrete mononuclear [BiCl₆]³⁻ and chloride anions. Tetrakis(2‐amino‐3‐methylpyridinium) di‐μ‐chlorido‐bis[tetrachloridobismuth(III)], (C₆H₉N₂)₄[Bi₂Cl₁₀], (2), tetrakis(2‐amino‐3‐methylpyridinium) di‐μ‐bromido‐bis[tetrabromidobismuth(III)], (C₆H₉N₂)₄[Bi₂Br₁₀], (3), and bis(4‐amino‐3‐ammoniopyridinium) di‐μ‐chlorido‐bis[tetrachloridobismuth(III)] dihydrate, (C₅H₉N₃)₂[Bi₂Cl₁₀]·2H₂O, (4), incorporate discrete [Bi₂X₁₀]⁴⁻ anions (X = Cl or Br), while catena‐poly[2,6‐diaminopyridinium [[cis‐diiodidobismuth(III)]‐di‐μ‐iodido]], {(C₅H₈N₃)[BiI₄]}_n, (5), and catena‐poly[2,6‐diaminopyridinium [[cis‐dibromidobismuth(III)]‐di‐μ‐bromido]], {(C₅H₇N₂)[BiBr₄]}_n, (6), include [Bi_nX_4n]ⁿ⁻ anionic chains (X = Br or I). Structures (2) and (3) are isostructural, while that of (5) is a pseudomerohedral twin. There is no discernible correlation between the type of anionic species obtained and the cation or halide ligand used. The Bi^III centres always have a slightly distorted octahedral geometry and there is a correlation between the Bi—X bond lengths and the number of classic N—H…X hydrogen bonds that the X ligand accepts, with a greater number of interactions corresponding with slightly longer Bi—X distances. The supramolecular networks formed by classic N—H…X hydrogen bonds include ladders, bilayers and three‐dimensional frameworks.

中文翻译：

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具有取代的氨基吡啶鎓阳离子的卤化铋（III）盐。

不同取代的氨基吡啶鎓阳离子的六种卤化铋（III）盐的晶体结构显示出离散的单核[BiCl ₆ ] ³⁻和双核[Bi ₂ X ₁₀ ] ⁴⁻阴离子（X = Cl或Br），以及聚合的顺式-双卤代-bridged [毕_ñ X _{4 ñ} ] ^{ñ -}阴离子链（X = Br或I）。双（2-氨基-3-氨基吡啶鎓）六氯化铋（III）一水合物，（C ₅ H ₉ N ₃）₂ [BiCl ₆ ] Cl·H ₂O（1）包含离散的单核[BiCl ₆ ] ^3-和氯离子。四（2-氨基-3-甲基吡啶）四（2-氨基-3-甲基吡啶鎓）双[四氯化铋（III）]，（C ₆ H ₉ N ₂）₄ [Bi ₂ Cl ₁₀ ]，（2），四（2-氨基-吡啶鎓） 3-甲基吡啶鎓）di-溴代双[四溴化铋（III）]，（C ₆ H ₉ N ₂）₄ [Bi ₂ Br ₁₀ ]，（3）和双（4-氨基-3-氨吡啶鎓）di -μ-氯代双[四氯铋（III）]二水合物，（C ₅ H ₉ N ₃）₂[Bi ₂ Cl ₁₀ ]·2H ₂ O，（4），掺入离散的[Bi ₂ X ₁₀ ] ⁴⁻阴离子（X = Cl或Br），而catena -poly [2,6-diaminopyridinium [[ cis - diiodidobismuth（ III）]-di-μ-碘]]，{（C ₅ H ₈ N ₃）[BiI ₄ ]} _n，（5）和catena -poly [2,6-diaminopyridinium [[ cis - dibromidobismuth（III） ]-di-μ-bromido]]，{（C ₅ H ₇ N ₂）[BiBr ₄ ]} _n，（6），包括[双_Ñ X _{4 Ñ} ] ^{ñ -}阴离子链（X = Br或I）。结构（2）和（3）是等结构的，而结构（5）的结构是伪面体孪晶。所获得的阴离子种类与所使用的阳离子或卤化物配体之间没有明显的相关性。Bi ^III中心始终具有稍微扭曲的八面体几何形状，并且Bi- X键的长度与X配体接受的经典N-H… X氢键的数量之间存在相关性，其中较大的相互作用对应于轻微的更长的Bi— X距离。由经典的NH… X氢键形成的超分子网络包括阶梯，双层和三维骨架。