
TY  - JOUR
A1  - Lawrance, GA 
A1  - Skelton, BW 
A1  - White, AH 
A1  - Wilkes, EN 
T1  - Tetraazacycloalkanes With Pendant Carboxylates. Copper(II)-Directed Syntheses and Crystal Structure of (Ethyl 1,5,9,13-tetraazabicyclo[11.2.2]heptadecane-7-carboxylate)copper(II) Perchlorate
JF  - Australian Journal of Chemistry
JO  - Aust. J. Chem.
Y1  - 1991
VL  - 44
IS  - 11
SP  - 1511
EP  - 1522
KW  - 
UR  - https://doi.org/10.1071/CH9911511 
N2  - Reaction of copper(II) complexes of the tetraamines H2N-(CH2)n-NH-(CH2)m-NH-(CH2)n-NH2 (n, m=5, 6), N,N&#8242;- bis (3-aminopropyl)-1,4-diazacyclohexane and ethane-1,2-diamine with formaldehyde and diethyl malonate in methanolic base produces macrocycles where initially new -NH-CH2-C( COOEt )2-CH2-NH-links are built by joining the cis-disposed primary amines in the precursor complexes. Under the basic conditions of the reaction, the macrocyclic product may be isolated not simply with gem ethoxycarbonyl groups, but as the carboxy ethoxycarbonyl, or even with a single carboxy pendant or its ester following ester hydrolysis and/or decarboxylation reactions. All diesters or acid esters can be hydrolysed conveniently to the stable monoacid in aqueous base, producing complexes of macrocyclic  tetraamines with a single carboxylate group pendant to the ring at the central carbon of a propyl chain. Physical properties of the copper(II) complexes are reported and compared with analogues where a nitro group is pendant to the ring rather than the carboxylate group. The (ethyl 1,5,9,13-tetraazabicyclo[11.2.2]heptadecane-7-carboxylate)copper(II) perchlorate monohydrate was crystallized in the monoclinic space group P 21/c, a 8.968(3), b 8.435(3), c 32.007(11)&#506;, &#946; 99.18(3)&#176;, Z = 4, and a single-crystal X-ray structure determination refined to R 0.045 for 2631 'observed' reflections. The copper ion exists in a square pyramidal geometry of four nitrogen donors and a perchlorate anion oxygen, with a quite short Cu-O distance (2.30&#506;). The Cu-N(secondary) and Cu-N(tertiary) distances are 2.037(4), 2.035(4), and 2.082(4), 2.062(4)&#506; respectively. 
ER  -

