Abstract: 5,5'-azotetrazole(2) was dissolved in distilled water reacted with an excess of diluted hydrochloric acid to produce 5-hydrazinotetrazolium chloride(3). 3 neutralized with sodium hydroxide to produce sodium 5,5'-Azotetrazole-5-Oxide pentahydrate(4). The structures of 3 and 4 were characterized by MS, <sup<1</sup<H NMR and <sup<13</sup<C NMR techniques, and the crystal structures of 3 and 4 were determined by X-ray single crystal diffraction analysis, 3 belongs to Monoclinic system with space group <em<P</em<2(1)/n and <em<a</em<=0.438(2) nm, <em<b</em<=2.395 6(2) nm, <em<c</em<=0.493 6(2) nm, <em<Z</em<=4, <em<V</em<=0.546(4) nm<sup<3</sup<, <em<D</em<<sub<c</sub<=1.659 g/cm<sup<3</sup<,<em<F</em<(000)=280; 4 belong to Triclinic system with space group P-1 and <em<a</em<=0.715 81(19) nm,<em<b</em<=0.766 3(2)nm,<em<c</em<=1.193 3(4) nm,<em<Z</em<=2,<em<V</em<=0.602 7(3)nm<sup<3</sup<,<em<D</em<<sub<c</sub<=1.742 g/cm<sup<3</sup<,<em<F</em<(000)=324.