Unexpected assembly of a cyanide-bridged one-dimensional nickel(II) complex with alternating [Ni(TIM)]2+ and [Ni(CN)4]2− ions (TIM=2,3,9,10-tetramethyl-1,4,8,11-tetraazacyclotetradeca-1,3,8,10-tetraene)

Crystals of a cyanide-bridged nickel(II) complex [Ni(TIM)][Ni(CN)4] (1) (TIM=2,3,9,10-tetramethyl-1,4,8,11-tetraazacyclotetradeca-1,3,8,10-tetraene) were formed by diffusion of [Ni(TIM)](ClO4)2 in MeCN and K3[Cr(CN)5(NO)] in H2O for two months. Complex 1 crystallized in the triclinic space group P-1 with a=7.610(2), b=8.096(2), c=9.392(2) Å, α=69.56(1), β=71.44(1), γ=84.66(2)°. The crystal structure confirmed the presence of cyanide-bridged nickel(II) chains. The [Ni(CN)4]2− moieties were shown to derive from the dissociation of [Cr(CN)5(NO)]3− and [Ni(TIM)]2+ owing to the stability of the [Ni(CN)4]2− ion. The coordination geometry around the six-coordinate nickel(II) ion is axially elongated octahedral with four nitrogen atoms of the macrocycle (Ni–N=2.008(2) Å) and two nitrogen atoms of the bridging cyanides (Ni–N=2.123(2) Å). The four-coordinate nickel(II) groups are square-planar with the Ni–C bond distances ranging from 1.858(2) to 1.861(3) Å.