Abstract
Syntheses of nickel(II) complexes of the pendant arm polyamines 10-methyl-1,4,8,12-tetraazacyclopentadecane-10-amine (L3) and 7-methyl-1,5,9,13-tetraazabicyclo[1.1.2.2]heptadecane-7-amine (L 5) as well as the pendant arm polyamino acids 1,4,8,12-tetraazacyclopentadecane-10-carboxylate (L 4) and 1,5,9,13-tetraazabicyclo[1.1.2.2]heptadecane-7-carboxylate (L 6) are described, as is the synthesis of the free ligand hydrochloride salts. All complexes form as purple octahedral paramagnetic species where coordination of the pendant arm is implied. The complex [Ni(L 6H −1)](ClO 4) crystallises in the monoclinic space group P2 case1 a , a = 10.807(8), b = 14.340(6), c = 11.789(3) A ̊ , β = 96.49(9)° . The nickel atom lies at the centre of a distorted octahedron of four secondary nitrogens and two carboxylate oxygens, one from the pendant of the macrocycle and the other bridging from the external oxygen of the carboxylate of an adjacent complex cation. The sharing of each carboxylate between its own and the next nickel centre persists throughout the lattice, leading to a one-dimensional chain compound where a C-pendant attached directly to the macrocyclic ring acts as the bridging group.
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