By using a neutral inner-salt-type dicarboxylate as coligand, a novel two-dimensional (2D) manganese(II) coordination polymer, [Mn(L)(N3)]ClO4·1/2H2O (L = 1,3-bis(3-carboxylatopyridinium)propane), was synthesized, and characterized by X-ray crystallography and magnetic measurements. The compound contains uniform MnII chains with simultaneous azide and carboxylate bridges between adjacent MnII ions. The formally negative chains are interlinked by the positively-charged 1,3-bis(pyridinium)propane spacer, and the spiral conformation of the spacer imports intriguing helical features to the resulting 2D network, in which [MnL] helices are connected by sharing metal centers with alternating centro- and C2-symmetry. The triple (azide)bis(carboxylate) bridge mediates overall antiferromagnetic coupling with J = −3.0 cm−1, as a result of the competition between the antiferromagnetic (carboxylate) and ferromagnetic (azide) pathways.
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