Copper(II) Compounds of 5-Alkyl-3,5,7-triazanonane-1,9-diamines and 3,10-Bisalkyl-1,3,5,8,10,12-hexaaza-cyclotetradecanes; the Structure of 1R,5S,8R,12S-{3,10-Bis(2-hydroxypropyl)-1,3,5,8,10,12-hexaaza-cyclotetradecane-N1,N5,N8,N12} copper(II) Perchlorate

Abstract

Preparations are reported for (3,10-bisalkyl-1,3,5,8,10,12-hexaazacyclotetradecane)copper(II) perchlorates (alkyl = propyl, 1-methylethyl, butyl, cyclohexyl, 2-(diethylammmonio)ethyl, 2-hydroxyethyl, 3- hydroxypropyl and 2-hydroxypropyl) by reaction of bis(ethane-1,2-diamine)copper(II) perchlorate with methanal, and alkylamines. The structure of {3,10-bis(2-hydroxypropyl)-1,3,5,8,10,12-hexa-azacyclotetradecane}copper(II) perchlorate is reported [C₁₄H₃₄Cl₂CuN₆O₁₀, monoclinic, space group P2₁/c, a 8·504(2), b 14·855(5), c 9·034(2) Å, β 98·99(2)°, Z 2, R₁ 0· 061 for 1667 reflections]. The centrosymmetrical cation has a mean Cu–N distance of 2·001(4) Å, with perchlorate ion oxygen atoms weakly coordinated in the axial sites with a Cu–O distance of 2·61(1) Å. The planar copper(II) macrocycle cations form stacks which are linked by N–H · · · O and 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(II) perchlorate compounds with the same 3-substituent alkyl groups (plus methyl, and ethyl, and also phenyl) are similarly prepared by using 1 mole proportion of the amine and 2 mole proportions of methanal