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Two new mononuclear compounds [Mn(3-Br-pydc)(H 2 O) 3 ] ( 1 ) and {[Mn(5-Br-pyc)(bipy)(H 2 O)(Cl)]·2H 2 O ( 2 ) (3-Br-H 2 pydc = 3-Br-pyridine-2,6-dicarboxylic acid, 5-Br-Hpyc = 5-Br-pyridine-2-carboxylic acid, bipy = 2,2′-bipyridine) have been synthesized by traditional solution reaction and hydrothermal reaction, respectively. In both compounds, the Mn II  center is six-coordinated in a distorted octahedral geometry, formed by one tridentate chelate 3-Br-pydc dianion and three water molecules in  1 , while the coordination sphere consists of one bidentate chelate 5-Br-pyc anion, one bipy, one water molecule, and one chloride anion in  2  (MnNO 5  for  1  and MnN 3 O 2 Cl for  2 ). O–H⋯O hydrogen bonds, Br⋯O halogen bonds, and/or π-π stacking assist in the construction of the three-dimensional (3D) network structures of  1  and  2 . Notably, the 5-Br-Hpyc ligand was generated  in situ  by decarboxylation of the 3-Br-H 2 pydc precursor under hydrothermal conditions. Variable-temperature magnetic susceptibility data in the 2–300 K temperature range indicate weak antiferromagnetic coupling in both  1  and  2 .

The syntheses, structures, and magnetic properties of two mononuclear manganese(II) complexes involving in situ hydrothermal decarboxylation