文摘
Herein, we report on the synthesis, isolation, and comprehensive characterization (m.p., ATR-IR/Raman, elemental analysis, 14N NMR) of tetraazidozincate anions [Zn(N3)4]2– in a series of [Ph4P]+ and [PNP]+ [PNP = bis(triphenylphosphine)iminium] salts. The phase polymorphism in [Ph4P]2[Zn(N3)4] was investigated by temperature-dependent Raman spectroscopy and by powder and single-crystal X-ray diffraction experiments, which indicate the occurrence of five room-temperature-stable, and one common high-temperature phase, besides two polymorphs of the acetonitrile solvate [Ph4P]2[Zn(N3)4]·MeCN. Moreover, the synthesis of zinc azide solvates Zn(N3)2·n solvent (solvent = DMSO, n = 1, 3/2, 3; MeCN, n = 2/3) is presented for the first time. Single-crystal X-ray structures of all new compounds were determined. For a better understanding of structure and bonding in E(N3)2, [E(N3)3]– and [E(N3)4]2– (E = Zn, Cd, Hg), theoretical calculations at the M06-2X/aug-cc-pVDZ level were carried out.
