A series of transition metal coordination complexes, [Zn-3(2-aptt)(2)(1,4-bdc)(2)](n) (1), [Zn-4(2-aptt)(4)(H(2)pma)(2)(H2O)(4)](n) (2), [Zn-2(2-aptt)(2)(3-pc)(2)(H2O)(4)] (3), and [Pb(2-ptt)](n) (4) were synthesized under solvothermal conditions using the pyridine containing mercapto-triazole ligand 2-apttH [4-amino-3-(2-pyridyl)-1H-1,2,4-triazole-5-thione] as a main building block. Their structures were determined by single-crystal X-ray diffraction analyses and further characterized by elemental analyses and IR spectroscopy. Notably, desamination reaction exists in the formation of complex 4, in which the ligand 2-apttH deaminated to generate the ligand 2-pttH(2) [3-(2-pyridyl)-1H-1,2,4-triazole-5-thione]. The four complexes exhibit structural diversity: complex 1 presents an interesting 3D framework, complexes 2 and 4 feature 2D networks, whereas complex 3 shows dinuclear structure. Moreover, the luminescent properties of complexes 1-4, the first and second ligands were also studied.