Copper(II) compounds of some nitro-substituted imine-triamine macrocycles: The structure of (aqua kappa(1)-O)-(13-ethyl-5,7,7-trimethyl-13 nitro-1,4,8,11-tetraazacyclotetradec-4-ene-kappa(4) -N-1,N-4,N-8,N-11)copper(II) perchlorate

摘要

Reactions of (4,6,6-trimethyl-3,7-diazanon-3-ene-1,9-diamine)copper(II) perchlorate with methanal and nitroethane (or nitropropane) yield the nitro-substituted imine-triamine azarnacrocyclic compounds (5,7,7,13 -tetramethyl- 13 -nitro- 1,4,8, 11 -tetraazacyclotetradec-4-ene)copper(II) [or (13-ethyl-5,7,7-trimethyl-13-nitro-1,4,8,11-tetraazacyclotetradec-4-ene)copper(II) perchlorate. Compounds of these cations [Cu(L)(ClO4)(2), -ZnCl4, [Cu(L)(A)](ClO4)(2), A = H2O, NH3 and [Cu(L)(X)]ClO4, X = NCS-, N-3(-), NO2-, were prepared. Aqua-(13-ethyl- 5,7,7-trimethyl-13-nitro-1,4,8,11-tetraazacyclotetradec-4-ene)copper(II) perchlorate has the copper(II) ion in tetrahedrally twisted (+/- 0.045(2) angstrom} square-planar coordination, with mean Cu-N-amine, = 2.019(4) angstrom and Cu-Ni in, = 1.918(2) angstrom. Oxygen of water {Cu-O = 2.279(2) angstrom} and perchlorate {Cu-O = 2.905(2) angstrom} occupy the axial sites, with the Cu displaced by 0.143(1) angstrom from the N-4 mean plane towards the water molecule. The cation has the IR,8S,11S configuration, with the nitro substituent and one of the gem methyl substituents axially oriented to the side of the CuN4 plane away from the water molecule. (c) 2005 Elsevier Ltd. All rights reserved.