A new high-nitrogen compound [Mn(ATZ)(H2O)(4)](.)2H(2)O (ATZ=5,5-azotetrazolate) was synthesized. Crystal structure and elemental, IR and thermal analyses were investigated in the present work. It crystallized in triclinic space group P-1 with lattice parameters a= 6.304(2) angstrom, b = 7.004(2) angstrom, c = 7.921(3) angstrom, alpha = 76.114(5)-, beta = 74.023(5)1, gamma = 69.254(4)degrees. TG-DTG and DSC measurements are employed to postulate the thermal decomposition mechanism. The thermal decomposition kinetics of the main exothermic reaction was investigated by non-isothermal method and obtained its enthalpy of decomposition and the probable kinetic mechanism. An attempt was made to incorporate the relation between thermal stability and the structure. (c) 2006 Elsevier B.V. All rights reserved.