COPPER(II) COMPOUNDS OF 5-ALKYL-3,5,7-TRIAZANONANE-1,9-DIAMINES AND 10-BISALKYL-1,3,5,8,10,12-HEXAAZACYCLOTETRADECANES - THE STRUCTURE OF YL)-1,3,5,8,10,12-HEXAAZACYCLOTETRADECANE-N-1,N-5, N-8,N-12)COPPER(II) PERCHLORATE

Preparations are reported for l-1,3,5,8,10,12-hexaazacyclotetradecane) copper(II) perchlorates (alkyl=propyl, 1-methylethyl, butyl, cyclohexy l, 2-(diethylammmonio)ethyl, 2-hydroxyethyl, 3-hydroxypropyl and 2-hyd roxypropyl) by reaction of bis(ethane-1,2-diamine)copper(Ir) perchlora te with methanal, and alkylamines. The structure of )-1,3,5,8,10,12-he xaazacyclotetradecane}copper(II) perchlorate is reported [C14H34C12CuN 6O10, monoclinic, space group P2(1)/c, a 8.504(2), b 14.855(5), c 9.03 4(2) Angstrom, beta 98.99(2)degrees, Z 2, R-1 0.061 for 1667 reflectio ns]. The centrosymmetrical cation has a mean Cu-N distance of 2.001(4) Angstrom, with perchlorate ion oxygen atoms weakly coordinated in the axial sites with a Cu-O distance of 2.61(1) Angstrom. The planar copp er(II) macrocycle cations form stacks which are linked by N-H ... O an d O-H ... O-ClO3 hydrogen bonds involving the extended 2-hydroxypropyl substituents, with no interaction between the copper(II) ion and the hydroxy groups. (5-Alkyl-3,5,7-triazanonane-1,9-diamine) copper(ll) pe rchlorate compounds with the same 3-substituent alkyl groups (plus met hyl, and ethyl, and also phenyl) are similarly prepared by using 1 mol e proportion of the amine and 2 mole proportions of methanal.