Structures and Magnetic Properties of Manganese(II) Compounds Based on Chains with Simultaneous Carboxylate and Pseudohalide Bridges

Various zwitterionic carboxylate ligands form Mn II coordination polymers with carboxylate and pseudo‐halide bridges mixed in different ways. With mono‐zwitterions, [Mn(N 3 ) 2 (L 1 )(H 2 O)] n and [Mn(N 3 ) 2 (L 2 )] n contains 1D chains with (μ‐1,1‐N 3 )(μ‐1,3‐OCO) and (μ‐1,1‐N 3 ) 2 (μ‐1,3‐OCO) bridges, respectively. With di‐zwitterions, [Mn(N 3 )(L 3 )] n (ClO 4 ) n forms a 2D network based on chains with (μ‐1,1‐N 3 )(μ‐1,3‐OCO) 2 bridges, whereas [Mn 2 (X) 4 (L 4 )] n · 2 n H 2 O (X = N 3 or NCO) are interpenetrating 3D networks based on chains with (μ‐1,1‐X) 2 (μ‐1,3‐OCO) bridges. With a tri‐zwitterion, [Mn 7 (N 3 ) 14 (OH) 2 (L 5 )(H 2 O) 6 ] n · 4 n H 2 O is a 2D network based on a novel chain in which μ‐1,1‐N 3 ‐ and μ‐1,3‐OCO‐bridged trinuclear motifs and μ 3 ‐OH‐ and μ‐1,1‐N 3 ‐bridged tetranuclear motifs are linked by μ‐1,3‐N 3 and μ 3 ‐1,1,3‐N 3 . All compounds exhibit antiferromagnetic interactions, the magnitude of which depends upon the nature and mixing mode of the bridges, and follow the trend (μ ‐ N 3 )(μ‐OCO) < (μ‐N 3 )(μ‐OCO) 2  < (μ‐N 3 ) 2 (μ‐OCO) < (μ‐NCO) 2 (μ‐OCO).