Two new coordination compounds Zn(AZT) 4 (H 2 O) 2 2 •4H 2 O and Zn(AZT) 2 (H 2 O) 4 2 •4H 2 O have been prepared by using AZT (3-azido-1,2,4-triazole) as ligands, PA -(picrate) or HTNR -(anion formed by the deprotonation of one of the two hydroxyl-groups of 2,4,6-trinitroresorcinol) as outer anions. The X-ray crystallographic data show that the central zinc(II) ion is coordinated by four N atoms of four AZT molecules and two O atoms of two H 2 O molecules in Zn(AZT) 4 (H 2 O) 2 2 •4H 2 O. In Zn(AZT) 2 (H 2 O) 4 2 •4H 2 O, six coordination-atoms come from two N atoms of two AZT molecules and four O atoms of four H 2 O molecules. The coordination sites of AZT ligands in both compounds are always 4-N atoms of the triazole rings. H 2 O molecules play vital roles in the formation of hydrogen bonds, which contribute to the construction of the crystal structures of both compounds. The offset face-to-face π-π stacking interactions existing in the crystal of Zn(AZT) 4 (H 2 O) 2 2 • 4H 2 O also contribute to the formation and stability of its crystal structure. TG-DTG and DSC analysis results show that the thermal decomposition processes of Zn(AZT) 2 (H 2 O) 4 2 •4H 2 O are milder than those of Zn-(AZT) 4 (H 2 O) 2 2 •4H 2 O due to the more coordination H 2 O molecules and less AZT ligands in the molecular unit of the former compound. Sensitivity tests reveal that Zn(AZT) 4 (H 2 O) 2 2 •4H 2 O has sensitive nature towards heat, whereas Zn(AZT) 2 (H 2 O) 4 2 •4H 2 O is insensitive; both compounds are insensitive to friction and impact.