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

N-rac-(5,7,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradeca-4,14(1)-diene)copper(II) perchlorate, [C16H32CuN4](ClO4)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–Namine = 1.994(1) and Cu–Nimine = 1.969(1) Å, with tetrahedral displacements of the N4 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-1:2κ2C:N;1:3κ2C:N-dicyano-1κ2C-bis(N-rac-5,7,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradeca-4,1(14)-diene-κ4N1,4,8,11)copper(II)–nickel(II) tetra(cyano-κ1C)nickelate(II), [(C16H32N4)Cu–NC–Ni(CN)2–CN–Cu(C16H32N4)] [Ni(CN)4], with Cu–Namine = 2.016(2), 2.002(2), Cu–Nimine = 1.964(2), 1.987(2) and axial Cu–Ncyano = 2.298(2) Å, Cu–NC = 142.1(2)°. The CuN4 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.

The cation of N-rac-(5,7,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradeca-4,14(1)-diene)copper(II) perchlorate has twofold symmetry with Cu–Namine = 1.994(1) and Cu–Nimine = 1.969(1) Å, and with weak off-axis interactions with perchlorate oxygen atoms, Cu–O = 3.017(1) Å. The structure is compared with those of homologues with 14–18 ring-members. The tetracyanonickelate(II) compound has a trinuclear tetracyanonickelate-bridged cation with mean Cu–Namine = 2.009(3), mean Cu–Nimine = 1.974(3), Cu–Ncyano = 2.298(2) Å and Cu–NcyanoC = 142.1(2)°.Figure optionsDownload as PowerPoint slide