Synthesis and Solid State Chemistry of CH₃BiI₂:  A Structure with an Extended One-Dimensional Organometallic Framework

Abstract

Red needle-like crystals of the title compound were grown using a reaction between Bi metal and methyl iodide under solvothermal conditions. CH3BiI2 crystallizes in the monoclinic space group C2/m with an unusual one-dimensional organic−inorganic chain-like structure. The Bi atoms have a square pyramidal local geometry, with four I atoms forming the base and one methyl group occupying an apical site. Each basal square shares trans edges with two nearest neighbors to form a one-dimensional inorganic BiI2 chain along the b-axis. All methyl groups are covalently bonded to bismuth atoms and are aligned on one side of the BiI2 basal plane. The organic−inorganic chains are held together via van der Waals interaction, forming an extended solid state structural array. Extended Hückel band structure calculations demonstrate electronic one-dimensionality for CH3BiI2. Molecular modeling suggests that the square pyramidal Bi coordination arises primarily to reduce Bi−C antibonding character in the HOMO. The resulting Bi 6s and 6p hybridization in the valence band (HOMO) leads to a stereochemically active lone pair oriented trans to each methyl group. Thermal stability and decomposition of the title compound is examined using GC mass spectroscopy and simultaneous TGA and DTA techniques. CH3BiI2 begins to decompose at 185 °C in an inert atmosphere into methyl iodide and bismuth monoiodide, providing a new pathway to the formation of the interesting low valency one-dimensional conductor, BiI.

Naturally Self-Assembled Nanosystems and Their Templated Structures for Photonic Applications

“…These self-assembling inorganic-organic perovskites adopt an alternating framework of semiconducting inorganic sheets and organic layers. The increasing interest is because of the ability to derive low-dimensional crystals, which show unique crystal structure and physical and optical properties, from parent 3D networks of AMX 3 from simple and effective natural self-assembly [32][33][34][35][36][37][38][39][40][41][42][43]. These materials involve different types of interactions allowing the assembly of complex and highly-ordered structures with various bonding schemes.…”

Synthese und Einkristallröntgenstrukturanalyse von Bromdi(isopropenyl)bismutan

“…Diiod(methyl)bismutan wurde auch auf direktem Wege aus metallischem Bismut und Methyliodid im Autoklaven erhalten [5]. Die Tri(organyl)bismutane ihrerseits werden durch Umset-zung von Bismut(III)-halogeniden mit den entsprechenden Grignard-oder Organolithiumverbindungen synthetisiert [19] [11] sind mo È glicherweise mit sterischen bzw.…”

“…Bisher sind nur wenige Einkristallro È ntgenstrukturbestimmungen von aliphatischen Organobismutverbindungen bekannt [3,4,5] und noch keine von einem aliphatischen Di(organyl)-halogenbismutan. Im Hinblick auf eine mo È gliche Verwendung von Halogenbismutanen als Synthesebausteine fu È r organometallische Makromoleku È le [6 a, 6 b] interessierte uns besonders die Darstellung von Bromdi(isopropenyl)bismutan (2).…”

Bismuth(III) Complexes with Bis(dimethylphenyl) Dithiophosphates: Synthesis, Characterization and Crystal Structure of [{(3,5-CH3)2C6H3O}2PS2]3Bi

“…12,13 Due to its non-toxic and non-carcinogenic nature, the use of bismuth compounds in medicine can be traced back to the middle ages, 14 although less consideration has been paid to bismuth chemistry in comparison with that of rest of the members of group 15 elements. In addition, chemistry of bismuth compounds has advanced considerably due to its potential in applications as precursors in material sciences, [15][16][17][18][19][20][21][22][23][24][25][26][27] as X-ray imaging agents 28 and as catalysts. 29 Further interest in the study of these compounds lies in their significance in medicinal chemistry.…”