N-rac-(5,7,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradeca-4,14(1)-diene)copper(II): Structures of the perchlorate salt and a trinuclear tetracyanonickelato-bridged compound

Abstract

N-rac-(5,7,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradeca-4,14(1)-diene)copper(II) perchlorate, [C 16H 32CuN 4](ClO 4) 2, is isostructural with the Ni(II) analogue. The cation has twofold symmetry (axis through Cu and the mid-points of the C2–C3 and C9–C10 bonds), with Cu–N amine = 1.994(1) and Cu–N imine = 1.969(1) Å, with tetrahedral displacements of the N 4 group of ±0.007(2) Å. The dimensions are compared with those of compounds of homologuous cations with 14–18 ring members. The cation forms a compound with a centrosymmetrical trinuclear tetracyanonickelate(II)-bridged cation di-μ-cyano-1:2κ 2C:N;1:3κ 2C:N-dicyano-1κ 2C-bis(N- rac-5,7,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradeca-4,1(14)-diene-κ 4N 1,4,8,11)copper(II)–nickel(II) tetra(cyano-κ 1C)nickelate(II), [(C 16H 32N 4)Cu–NC–Ni(CN) 2–CN–Cu(C 16H 32N 4)] [Ni(CN) 4], with Cu–N amine = 2.016(2), 2.002(2), Cu–N imine = 1.964(2), 1.987(2) and axial Cu–N cyano = 2.298(2) Å, Cu–N C = 142.1(2)°. The CuN 4 group of the azamacrocycle is appreciably bent { transN–Cu–N = 160.30(7)°, 178.25(2)°}, with the Cu displaced towards the axial cyano nitrogen.