Two Extended 5‐Methyltetrazolate‐Based Magnetic Complexes: Synthesis, Structure, and Magnetic Properties

Two 5‐methyl‐tetrazolate (mtz – )‐based paramagnetic metal coordination polymers, {[Cu 2 (H 2 O) 2 (mtz)(μ 3 ‐OH)(nip)] · H 2 O} n ( 1 ) and [Cu(H 2 O)(mtz) 2 ] n ( 2 ), were obtained in the presence and absence of aromatic 5‐nitroisophathalate (nip 2– ) coligand by varying the preparation methods. Structural determinations reveal that 1 is a three‐dimensional (3D) framework with corner‐sharing triangular ribbons infinitely extended by ditopic nip 2– connectors. In contrast, 2 is a coplanar (4,4) layer constructed from square‐pyramidal Cu II ions and μ‐N1,N4‐mtz – linkers, which is further assembled into a 3D supramolecular network by interlayer hydrogen‐bonding interactions. Magnetically, spin‐frustrated antiferromagnetic ordering is observed in the 3D framework of 1 and canted antiferromagnetic behavior with a slight spin‐flop transition is presented in 2 , which are structurally resulting from the locally Δ‐ribbon in 1 and asymmetric magnetic superexchange mediated by the μ‐N1,N4‐mtz – bridge of 2 .