A Second Polymorphic Form of Trimethylindium:  Topology of Supramolecular Architectures of Group 13 Trimethyls

Abstract

Crystallization of Me 3 In from hexane solution at ambient temperature allows for the isolation of a new phase that cannot be obtained by classical sublimation routes. The crystal structure analysis revealed that this new polymorph of Me 3 In crystallizes in the rhombohedral space group R3 h. The primary structural effect of the In-CH 3 ‚‚‚In intermolecular interactions results in the formation of cyclic hexamers with 12-membered (InC) 6 rings of an extended-chair conformation. The shortest intermolecular In‚‚‚C contact is 3.028(4) Å with In‚‚‚H distances between 2.74 and 2.79 Å. The hexamers are further linked by longer In-CH 3 ‚‚‚In bridges into the 3D network. In addition, the tetragonal form of Me 3 In was redetermined at 100 K. The presented results demonstrate that the impact of both crystallization conditions and the character of intermolecular forces on clustering events is evident. Finally, the network topology of a family of the group 13 trimethyls is analyzed and correlated.

Solid-State Structures of Trialkylbismuthines BiR3 (R = Me, i-Pr)

“…The formation of a metal–metal-bonded dimer is unusual for main-group-metal–methyl complexes. For instance, Lewis acidic group 13 metal trialkyls MMe 3 form Me-bridged dimers (AlMe 3 ), ladderlike pseudopolymers, or pseudotetramers (GaMe 3 , InMe 3 , TlMe 3 ) due to the formation of two-electron–three-center bonds . The same is true for BeMe 2 , which adopts a polymeric chainlike structure, and even ZnMe 2 shows weak intermolecular Zn···Me contacts in the solid state .…”

Reactivity of (C5Me5)2UMe2 and (C5Me5)2UMeCl toward Group 13 Alkyls

“…For comparison, the In−C distances in the two different polymorphs of InMe 3 range from 2.149(5) to 2.173(3) Å with the In atoms located only 0.0701(2) Å above the ligand plane . Interestingly, the In···C(μ-Me) distances of the U−CH 3 ···In linkages average 2.890 Å, which is considerably shorter than the intermolecular In···C contacts in pure InMe 3 (3.028(3)−3.409(4) Å) . This shorter contact might indeed be the driving force for the formation and crystallization of compound 1b .…”

Stepwise Stress‐Induced Transformations of Metal‐Organic Polyhedral Cluster‐Based Assemblies: Where Conformational and Supramolecular Features Meet

“…Our groups have a long‐standing interest in the elucidation of factors controlling self‐organization processes of metal complexes, [33,39,43] the design and construction of porous molecular crystals, [27,33,40,41,44] the investigation on dynamics of supramolecular networks, [45–48] and the search for new polymorphs [49–51] . Based on these experiences, we purposefully selected a polyhedral zinc‐oxo cluster incorporating monoanionic N , N’ ‐diphenylformamidinate ( dipf ) ligands, [(μ 4 −O)Zn 4 ( dipf ) 6 ] ( 1 ).…”