The substituted macrocycle 6,13-dimethyl-1,4,8,11- tetraazacyclotetradecane-6,13-diamine (L) can be crystallized as the perchlorate salt or the zinc dithionate complex. The crystal structures of [H4L](ClO4)4.6H2O (1) and [Zn(H2L)(S2O6)2].4H2O (2) have been determined by X-ray diffraction methods and refined to a residual of 0.058 for 1926 independent observed reflections for (1) and 0.022 for 2122 independent reflections for (2). The crystals of (1) are monoclinic, P21/c, a 10.657(2), b 12.466(7), c 12.216(3)Ǻ, β 96.73(2)° and those of (2) are monoclinic, P21/c, a 8.521(1), b 12.990(1), c 12.731(1)Ǻ,β 105.45(1)°. The pendant primary amines in the zinc(II) complex of L are protonated and not coordinated, with conformational geometry very similar in both structures.