Propylene-1,3-diamine and 2-chlorobenzaldehyde react together in the presence of copper and formic acid to produce the 32-membered octaaza-tetraimine macrocycle 7,8,16,17,18,27,28,36,37,38-decahydrotetrabenzo- [g,o,w,aw][1,5,9,13,17,21,25,29]octaazacyclodotriacontine (8) in 26% yield. Reduction of 8 with cyanoborohydride in acetic acid-methanol produces the corresponding 32-membered octaaza-octaamine 7,8,9,10,16,17,18,19,20,27,28,29,30,36,37,38,39,40-octadecahydrotetrabenzo [g,o,w,ae][1,5,9,13,17,21,25,29]octaazacyclodotriacontine (9). In chloroform 8 rearranges into an equilibrium mixture of the 16-membered cyclic tetraaza-diimine 5,7,8,16,17,18-pentahydrodibenzo[g,o][1,5,9,13]tetraazacyclotetradecine (4) and the 24-membered hexaaza-triimine 7,8,16,17,18,27,28-heptahydrotribenzo[g,o,w][1,5,9,13]hexaazacyclotetracosine (6). The macrocycle 4 was separated as its nickel(II) thiocyanate derivative and subsequently displaced with cyanide. Reduction of 4 with cyanoborohydride afforded the 16-membered tetraaza-tetraamine 7,8,9,10,16,17,18,19,20-nonahydrodibenzo- [g,o][1,5,9,13]tetrazacyclotetradecine (5). The hexaaza-triimine 6 was trapped by precipitation, isolated by fractional crystallization, and subsequently converted into the 24-membered hexaaza-hexaamine 7,8,9,10,16,17,18,19,20,27,28,29,30-tridecahydrotribenzo[g,o,w][1,5,9,13,17,21]hexaazacyclotetracosine (7) by reduction with cyanoborohydride. The structures of the paramagnetic salts [Cu-2(9)](CF3SO3)(4).3H2O and [Cu(7-H)](CF3SO3)(3).MeOH.2H(2)O have been determined. Data for [Cu-2(9)](CF3SO3)(4).3H(2)O : space group P2(1)/n, a = 14.940(3) Angstrom, b = 9.825(2) Angstrom, c = 20.456(2) Angstrom, beta = 97.58(1)degrees, R = 0.058, R(w) = 0.064. Data for [Cu(7-H)](CF3SO3)(3). MeOH.2H(2)O : space group P1 (No. 2), a = 11.509(3) Angstrom, b = 12.172(3) Angstrom, c = 18.129(4) Angstrom, alpha = 82.23 degrees, beta = 83.58 degrees, gamma = 72.47 degrees, Z = 2, R = 0.059, R(w) = 0.069. The copper ions in each structure have regular square-planar geometries.