trans‐Dioxocyclam (1,4,8,11‐tetraazacyclotetradecane‐2,9‐dione) dihydrate and its NiII complex

The crystal structures are reported of trans‐dioxocyclam dihydrate, C₁₀H₂₀N₄O₂·2H₂O, a structural isomer of the well known cis‐dioxocyclam, and of its novel Ni complex, (1,4,8,11‐tetra­aza­cyclo­tetra­decane‐2,9‐dionato‐κ⁴N)­nickel(II) dihydrate, Ni(C₁₀H₁₈N₄O₂)]·2H₂O, the first example of a trans­ition metal complex of this ligand. Both mol­ecules lie on crystallographic centres of inversion. The free ligand has two of its N atoms turned outwards from the ring and hydrogen bonded to water mol­ecules. A major conformational change takes place in the complex in which the ligand binds in a trans tetradentate fashion, as suggested by the electronic spectrum. The nickel(II) ion is low spin, although the electronic spectrum of the complex in water indicates an equilibrium mixture of low‐spin and high‐spin species. The irreversible electrochemical oxidation of NiL¹] (L¹ is deprotonated trans‐dioxocyclam, C₁₀H₁₈N₄O₂) in water occurs at a potential of 0.964 V versus SHE (standard hydrogen electrode)], which is very similar to that for the Ni–cis‐dioxocyclam complex.