A rare case of solution and solid state inter-conversion of two copper(II) dimers and a copper(II) chain

Three Cu(II)-azido complexes of formula [Cu2L2(N3)2] (1), [Cu2L2(N3)2]·H2O (2) and [CuL(N3)]n (3) have been synthesized using the same tridentate Schiff base ligand HL (2-[(3-methylaminopropylimino)-methyl]-phenol), the condensation product of N-methyl-1,3-propanediamine and salicyldehyde). Compounds 1 and 2 are basal-apical μ-1,1 double azido bridged dimers. The dimeric structure of 1 is centrosymmetric but that of 2 is non-centrommetric. Compound 3 is a μ-1,1 single azido bridged 1D chain. The three complexes interconvert in solution and can be obtained in pure form by carefully controlling the synthetic conditions. Compound 2 undergoes an irreversible transformation to 1 upon dehydration in the solid state. The magnetic properties of compounds 1 and 2 show the presence of weak antiferromagnetic exchange interactions mediated by the double 1,1-N3 azido bridges (J = −2.59(4) and −0.10(1) cm−1, respectively). The single 1,1-N3 bridge in compound 3 mediates a negligible exchange interaction.