Andriichuk Irina L, Tsymbal Liudmyla V, Arion Vladimir B, Lampeka Yaroslaw D
L. V. Pisarzhevskii Institute of Physical Chemistry of the National Academy of Sciences of Ukraine, Prospekt Nauki 31, 03028 Kiev, Ukraine.
Institute of Inorganic Chemistry of the University of Vienna, Wahringer Str., 42, 1090 Vienna, Austria.
Acta Crystallogr E Crystallogr Commun. 2019 Jun 21;75(Pt 7):1015-1019. doi: 10.1107/S2056989019008387. eCollection 2019 Jul 1.
The asymmetric units of the title compounds, -di-aqua-(3-benzyl-1,3,5,8,12-penta-aza-cyclo-tetra-decane-κ , , , )copper(II) isophthalate monohydrate, Cu(CHN)(HO)·HO, (I), and -di-aqua-[3-(pyridin-3-ylmeth-yl)-1,3,5,8,12-penta-aza-cyclo-tetra-decane-κ , , , ]copper(II) iso-phthalate 0.9-hydrate, Cu(CHN)(HO)·0.9HO, (II) consist of one di-aqua macrocyclic cation, one di-carboxyl-ate anion and uncoordinated water mol-ecule(s). In each compound, the metal ion is coordinated by the four secondary N atoms of the macrocyclic ligand and the mutually O atoms of the water mol-ecules in a tetra-gonally distorted octa-hedral geometry. The average equatorial Cu-N bond lengths are significantly shorter than the average axial Cu-O bond lengths [2.020 (9) 2.495 (12) Å and 2.015 (4) 2.507 (7) Å for (I) and (II), respectively]. The coordinated macrocyclic ligand in the cations of both compounds adopts the most energetically favorable -III conformation. In the crystals, the complex cations and counter-anions are connected hydrogen-bonding inter-actions between the N-H groups of the macrocycles and the O-H groups of coordinated water mol-ecules as the proton donors and the O atoms of the carboxyl-ate as the proton acceptors. Additionally, as a result of O-H⋯O hydrogen bonding with the coordinated and water mol-ecules of crystallization, the isophthalate dianions form layers lying parallel to the (01) and (100) planes in (I) and (II), respectively.
标题化合物一水合邻苯二甲酸 - 二水合 -（3 - 苄基 - 1,3,5,8,12 - 五氮杂环十四烷 - κ(^{N1})，(^{N3})，(^{N5})，(^{N7})）铜（II），Cu(C₁₄H₂₄N₅)(H₂O)₂·H₂O，（I）和0.9水合邻苯二甲酸 - 二水合 - [3 -（吡啶 - 3 - 基甲基）- 1,3,5,8,12 - 五氮杂环十四烷 - κ(^{N1})，(^{N3})，(^{N5})，(^{N7})]铜（II），Cu(C₁₃H₂₂N₅)(H₂O)₂·0.9H₂O，（II）的不对称单元由一个二水合大环阳离子、一个二羧酸根阴离子和未配位的水分子组成。在每个化合物中，金属离子由大环配体的四个仲氮原子和水分子的相互(O)原子以四方畸变八面体几何构型配位。平均赤道Cu - N键长明显短于平均轴向Cu - O键长[（I）和（II）分别为2.020（9） 2.495（12）Å和2.015（4） 2.507（7）Å]。两种化合物阳离子中的配位大环配体均采用能量上最有利的 - III构象。在晶体中，配合物阳离子和抗衡阴离子通过大环的N - H基团与配位水分子的O - H基团之间的氢键相互作用相连，其中大环的N - H基团作为质子供体，羧酸根的O原子作为质子受体。此外，由于与配位水分子和结晶水分子形成O - H⋯O氢键，邻苯二甲酸根二阴离子在（I）和（II）中分别形成平行于（01）和（100）平面的层。
