TriorganoazidometalatesCompounds with Unusual Structural Motifs

Abstract

The reaction of Ga(CH2Ph)3 with CsN3 in THF gives, after recrystallization from toluene, the metalate [Cs(toluene)0.5{(PhCH2)3GaN3}] (1), whereas the corresponding reaction of In(CH2Ph)3 with CsN3 in THF yields, after recrystallization from toluene, the solvent-free salt Cs[(PhCH2)3InN3] (2). 1 and 2 have been characterized by NMR, IR, and MS techniques as well as by X-ray analyses. According to the X-ray structure determination, 1 and 2 can be described as coordination polymers [1]n and [2]n in the solid state. [1]n consists of layers, packed along the crystallographic a-axis. The monomers 1 are connected by Cs···N3 and Cs···aryl contacts to form polymeric sheets. [2]n mainly consists of chains aligned along the directions [011] and [011̄]. Here, the monomers 2 are connected by Cs···phenyl contacts. In addition, weak In···N3 interactions of 2.901(5) Å are observed, leading to a strongly distorted trigonal bipyramidal coordination sphere of the indium center (angular sum, equatorial plane, 355°) and to a cross-linking of the chains in the direction [100].