Crystal structures of trans-di­aqua­(3-R-1,3,5,8,12-penta­aza­cyclo­tetra­deca­ne)copper(II) isophthalate hydrates (R = benzyl or pyridin-3-ylmethyl)

The asymmetric units of the title compounds, trans-di­aqua­(3-benzyl-1,3,5,8,12-penta­aza­cyclo­tetra­decane-κ(4) N (1),N (5),N (8),N (12))copper(II) isophthalate monohydrate, [Cu(C(16)H(29)N(5))(H(2)O)(2)](C(8)H(4)O(4))·H(2)O, (I), and trans-di­aqua­[3-(pyridin-3-ylmeth­yl)-1,3,5,8,12-penta­aza­cyclo­tetra­decane-κ(4) N (1),N (5),N (8),N (12)]copper(II) iso­phthalate 0.9-hydrate, [Cu(C(15)H(28)N(6))(H(2)O)(2)](C(8)H(4)O(4))·0.9H(2)O, (II) consist of one di­aqua macrocyclic cation, one di­carboxyl­ate anion and uncoordinated water mol­ecule(s). In each compound, the metal ion is coordinated by the four secondary N atoms of the macrocyclic ligand and the mutually trans O atoms of the water mol­ecules in a tetra­gonally distorted octa­hedral geometry. The average equatorial Cu—N bond lengths are significantly shorter than the average axial Cu—O bond lengths [2.020 (9) versus 2.495 (12) Å and 2.015 (4) versus 2.507 (7) Å for (I) and (II), respectively]. The coordinated macrocyclic ligand in the cations of both compounds adopts the most energetically favorable trans-III conformation. In the crystals, the complex cations and counter-anions are connected via hydrogen-bonding inter­actions between the N—H groups of the macrocycles and the O—H groups of coordinated water mol­ecules as the proton donors and the O atoms of the carboxyl­ate as the proton acceptors. Additionally, as a result of O—H⋯O hydrogen bonding with the coordinated and water mol­ecules of crystallization, the isophthalate dianions form layers lying parallel to the ([Image: see text]01) and (100) planes in (I) and (II), respectively.