Halobismuth(III) salts with substituted aminopyridinium cations

Abstract

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 [BinX4n]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 [BinX4n]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 BiIII 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.

The Pnictogen Bond, Together with Other Non-Covalent Interactions, in the Rational Design of One-, Two- and Three-Dimensional Organic-Inorganic Hybrid Metal Halide Perovskite Semiconducting Materials, and Beyond

“…Senior and coworkers [ 157 ] have reported the crystal structures of six halobismuth(III) salts of a variety of substituted aminopyridinium cations. These crystals feature discrete mononuclear [BiCl 6 ] 3− and binuclear [Bi 2 X 10 ] 4− anions (X = Cl or Br), and polymeric cis -double-halo-bridged [Bi n X 4 n ] n − anionic chains (X = Br or I).…”

“… Ball-and-stick and polyhedral models of selected 1D structure. ( a ) bis(N 1 ,N 1 -diethylethane-1,2-bis(aminium)) bis(μ-bromo)-octabromo-di-antimony (C 6 H 18 N 2 2+ ) 2 (Br 10 Sb 24 − ) [ 154 ]; ( b ) pentakis(methylammonium) tris(μ-iodo)-hexakis(iodo)-di-lead bis(methylamine) (CH 6 N + ) 5 (I 9 Pb 2 5− ),2(CH 5 N) [ 155 ]; ( c ) bis(3-ammoniumyl-4-amino-pyridin-1-ium) bis(μ-chloro)-octachloro-di-bismuth dehydrate (C 5 H 9 N 3 2+ ) 2 (Bi 2 Cl 10 4− )2(H 2 O) [ 156 , 157 ]; ( d ) catena-[methylammonium bis(μ-iodo)-iodo-lead monohydrate (CH 6 N + )(I 3 Pb − ) n ,(H 2 O) [ 158 ]. Intermolecular contacts between bonded atomic basins are illustrated as dotted lines in cyan and hanging contacts in red.…”

Influence of crystal structure and composition on optical and electronic properties of pyridinium-based bismuth iodide complexes

“…1,17–21 Halobismuthate( iii ) anions of various organic salts form simple discrete mononuclear [BiX 6 ] 3− structures, to more complicated binuclear [Bi 2 X 10 ] 4− and multinuclear anions such as [Bi 4 I 16 ] 4− , [Bi 4 Br 18 ] 6− , [Bi 5 Cl 18 ] 3− , [Bi 6 I 22 ] 4− , [Bi 6 Cl 26 ] 8− , [Bi 7 I 24 ] 3− and [Bi 8 Cl 28 ] 4− , and [Bi 2 X 9 ] 3− . 22,23 The main factor that determines the structure and topology of the halobismutate( iii ) fragments is the weak interaction between bismuth-based building blocks and cations.…”

“…16 In parallel, a wide range of bismuth(III) complexes has been reported, with several finding applications in photovoltaic and neuromorphic computing devices. 1,[17][18][19][20][21] 22,23 The main factor that determines the structure and topology of the halobismutate(III) fragments is the weak interaction between bismuth-based building blocks and cations.…”