Synthesis,crystal Structure And Properties Study Of Azo Triadimefon Compounds

In this paper,five salts of 4,4'-azo-1,2,4-triazol-5-one with sodium,magnesium,aminoguanidine,diaminoguanidine and triaminoguanidine were prepared.The single crystals of five salts were grown by slow evaporation,and their crystal structures were measured by single-crystal diffraction.[Na2(ZTO)-4H2O]n:orthorhombic,Pbca,its density is 1.768 g·cm-3,each Na cation is octahedrally coordinated by six oxygen atoms;[Mg(H2O)6](ZTO)2·4H2O:monoclinic,C2/c,its density is 1.633 g·cm-3,each Mg cation is octahedrally coordinated by six oxygen atoms;AG(ZTO)·H2O:triclinic,P-1,its density is 1.531 g.cm-3;DAG(ZTO)·2H20:triclinic,P-1,its density is 1.608 g·cm-3;TAG(ZTO)·H2O:triclinic,P-1·its density is 1.482 g·cm-3.The thermal behaviors of ZTO and ZTO salts were studied by DSC and TG,and the order of decomposition temperature is ZTO>[Na2(ZTO)·4H2O]n>G(ZTO)·H2O>AG(ZTO)·H2O>DAG(ZTO)·2H2O>TAG(ZTO)·H2O>[Mg(H20)6](ZTO)2·4H2O.The results showed that all above have good thermal stability,that the decomposition temperatures of ZTO salts are lower than ligand ZTO due to introducing cation,and that as to guanidine salts,the thermal decomposition temperature reduce with the increasing number of amino groups.According to thermal decomposition kinetics theory,the thermal decomposition kinetics equations of five ZTO salts were obtained.In order to obtain thermophysical property data,the specific heat capacity for compounds were measured,and the relationship between Cp and T were obtained.The constant-volume combustion heats(?&U for guanidine salts were measured,the ??U for guanidine salts are ordered as TAG(ZTO)>DAG(ZTO)>AG(ZTO),which tend to increase with the increasing number of amino groups.The standard molar enthalpy of formation(?fH?m)of guanidine salts can be calculated with Hess's law.To evaluate thermal safety of ZTO salts,the self-accelerating decomposition temperature(Te0),thermal ignition temperature(Tbe0),critical temperature of thermal explosion(Tbp0),adiabatic time-to-explosion(tTIAD),entropy of activation(?S?),enthalpy of activation(?H?)and free energy of activation(AG?)were calculated.The impact sensitivities(IS)of five salts were also measured.