Spectroscopic studies of triphenyltin azide and of its adducts with O- andN-donor ligands; the crystal and molecular structures of triphenyltin azide and of azido(hexamethylphosphoramide)triphenyl

Complete far-IR and Raman data (<400 cm(-1)) are reported for triphenyltin azide (1) as well as for adducts Ph3SnN3. L (L = hexamethylphosphoramide (H MPA), triphenylphosphine oxide, pyridine-N-oxide, 4-picoline-N-oxide, or py ridine). The small changes in v(Sn-N-3) noted on going from (1) to the addu cts, as well as solid-state Sn-119 nmr data, indicate that (1), like the ad ducts, has five-coordinate tin atoms. X-ray analysis shows that (1) crystal lizes with two different chains of five-coordinate Ph3Sn units joined by 1, 3-azide bridges. In one unit, the geometry around tin is similar to that fo und for the monomeric HMPA adduct (2), which has trans-axial HMPA and azide ligands. The other unit in (1) has nonplanar -SnC3- groups connected by le ss symmetric 1,3-azide bridges and thus resembles the structure of isoelect ronic triphenyltin isocyanate.