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 K-3 [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) Angstrom, alpha = 69.56(1), beta = 71.44(1), gamma = 84.66(2)degrees. 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) Angstrom) and two nitrogen atoms of the bridging cyanides (Ni-N = 2.123(2) Angstrom). The four-coordinate nickel(II) groups are square-planar with the Ni-C bond distances ranging from 1.858(2) to 1.861(3) Angstrom. (C) 2000 Elsevier Science S.A. All rights reserved.