Synthesis, crystal structures and luminescent properties of manganese and zinc complexes with in situ ligand formation of 3-amino-4-(5-tetrazolyl)-1H-pyrazole

Three metal–organic frameworks, [Mn(HL)(N3)] (1), [Mn(HL)Cl(H2O)] (2) and [Zn2(L)2(H2O)] (3) where H2L = 3-amino-4-(5-tetrazolyl)-1H-pyrazole, have been yielded through in situ hydrothermal reactions of manganese(II) or zinc(II) salts, NaN3 and 3-amino-4-cyano-1H-pyrazole (HACP). The crystal structure analysis reveals that 1–3 have different dense 3D frameworks with Schläfli symbols of {3·42·52·6}{32·43·54·66} for 1 which is an unprecedented (4,6)-connected framework, {4·122}2{42·124} for 2 which is a typical sqc519 structure, and {42·6}2{44·62·88·10} for 3 which is a typical ant/anatase structure, respectively. The ligand takes three different coordination modes in 1–3 as 3- or 4-connector. In addition, the photoluminescence of complex 3 was studied in solid state at room temperature, together with its thermal analysis.