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

摘要

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-N-amine=1.994(1) and Cu-N-imine=1.969(1) angstrom, with tetrahedral displacements of the N-4 group of +/- 0.007(2) angstrom. 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 tetracyanonickel ate(II) -bridged cation di-mu-cyano-1:2 kappa C-2:N;1:3 kappa C-2:N-dicyano-1 kappa C-2-bis(N-rac-5,7,7,12,12,14-hexamethyl-1,4,8,1 1-tetraazacyclotetradeca-4,1(14)-diene-kappa(4) N-1,N-4,N-8,N-11)copper(II)-nickel(II) tetra(cyano-kappa C-1)nickelate(II), [(C16H32N4)Cu-NC-Ni(CN)(2)-CN-Cu(C16H32N4)] [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) angstrom, Cu-N equivalent to C=142.1(2)degrees. The CuN4 group of the azamacrocycle is appreciably bent {transN-Cu-N=160.30(7)degrees, 178.25(2)degrees}, with the Cu displaced towards the axial cyano nitrogen. (C) 2005 Elsevier Ltd. All rights reserved.