Solid State Structure of Bi(N3)3, Bi(N3)3·Solvates and the Structural Dynamics in the [Bi(N3)6]3– Anion

Abstract

The highly explosive bismuth triazide, Bi(N3)3, was obtained in pure form by the reaction of BiF3 with Me3SiN3 in acetonitrile under solvothermal conditions at temperatures between 90 and 100 °C. X-ray, (14)N NMR, infrared, and Raman spectra are discussed along with the data for the acetonitrile, acetone, and dmso adducts. The influence of the solvent on the purity of the azide products is studied in detail for Bi(N3)3 and the [Bi(N3)6](3-) ion. Moreover, temperature dependent structural dynamics in the [Bi(N3)6](3-) ion, which is caused by small changes in the local environment around the [Bi(N3)6](3-) ion in the solid state, was studied by temperature variable single crystal X-ray and Raman studies. The azido-chlorido ligand back exchange was studied in detail by NMR techniques in [Bi(N3)6](3-) and Bi(N3)3 when chlorinated solvents such as CH2Cl2 were utilized leading to the formation of CH2(N3)Cl and/or HN3 along with partially chlorinated bismuth azides.