Syntheses, Crystal Structures, and Magnetic Properties of Two Mn(II) Coordination Polymers Based on the 5-Aminotetrazole Ligand: Effect of Sources of Ligand on Construction of Topological Networks

Two new Mn(II) coordination polymers, [Mn₁₅(atz)₁₈(μ₃-OH)₄(μ₃-SO₄)₄]_n·9nH₂O (1) and [Mn₈(atz)₄(μ-OH)₄(μ₄-SO₄)₄(H₂O)₄]_n·nH₂O (2) (atz = 5-aminotetrazolate), have been prepared under similar hydrothermal conditions except the difference of the source of the atz ligand. They were characterized by single-crystal X-ray diffraction studies, variable temperature (1.8−300 K) magnetic measurements, and thermal gravity analysis. The results of X-ray crystallographic analysis reveal that compound 1 is a 3D coordination polymer with a (3,4)-connected (8³)₄(8⁶)₃ topology, which is built from trinuclear [Mn₃(μ₃-SO₄)(μ₃-OH)] clusters and bridging mononuclear Mn centers. In compound 2, it contains a 3D inorganic cationic [Mn₈(μ₃-OH)₄(μ₄-SO₄)₄]_n⁴⁺ network with an unprecedented (4,6)-connected topological net, the Schläfli symbol of which is (3³·8²·9)₂(3⁶·8⁴·9⁵). The inorganic cationic net is templated by the atz ligands to form a microporous framework with hydrophilic channels. The variable temperature magnetic data indicate that 1 exhibits antiferromagnetic behavior, whereas 2 shows ferrimagnetic behavior.