Tsymbal Liudmyla V, Andriichuk Irina L, Stoica Alexandru-Constantin, Lampeka Yaroslaw D
L. V. Pisarzhevskii Institute of Physical Chemistry of the National Academy of Sciences of Ukraine, Prospekt Nauki 31, 03028, Kyiv, Ukraine.
"Petru Poni" Institute of Macromolecular Chemistry, Aleea Gr. Ghica Voda 41A, RO 700487, Iasi, Romania.
Acta Crystallogr E Crystallogr Commun. 2025 May 2;81(Pt 6):458-463. doi: 10.1107/S2056989025003792. eCollection 2025 Jun 1.
The asymmetric unit of the complex [3,10-bis-(3-carb-oxy-prop-yl)-1,3,5,8,10,12-hexa-aza-cyclo-tetra-decane-κ , , , ]di-chlorido-copper(II), [CuCl(CHNO)] or [Cu(H )Cl] (), consists of a centrosymmetric macrocyclic Cu dication and a chloride anion. The components of the heterometallic compound poly[[aqua-[μ-3,10-bis-(3-carb-oxy-prop-yl)-1,3,5,8,10,12-hexa-aza-cyclo-tetra-dec-ane-κ , , , :κ ,':κ '',''']-μ-chlorido--copper(II)cadmium(II] 1.25-hydrate], {[CuCd(CHNO)Cl(HO)]·1.25HO} or {[CuCd()(HO)Cl]·1.25HO} () are [Cu()(HO)] moieties coordinated to CdCl units the deprotonated carb-oxy-lic groups of the macrocycle, and four water mol-ecules of crystallization with partial occupancies. In each compound, the Cu ion coord-inates in the equatorial plane by the four secondary N atoms of the macrocyclic ligand, which adopts the most energetically stable -III conformation, and two mutually axial ligands in tetra-gonally elongated -CuNCl and -CuN(HO)Cl octa-hedral geometries in and , respectively. The coordination environment of the Cd ion in is a CdOCl distorted octa-hedron formed by two bidentately coordinated deprotonated carb-oxy-lic groups of different macrocycles and two chloride anions, one of which displays a μ-bridging function between the Cu and Cd ions. The extended structures of both complexes are distinctly lamellar. In particular, due to hydrogen-bonding inter-actions with participation of carb-oxy-lic groups, chloride atoms and secondary amino groups of the macrocycle, the electro-neutral mol-ecules in crystal of are arranged in chains running in the [101] direction; hydrogen bonding between the chains leads to layers parallel to the (101) plane. In crystal of , polymeric chains running along the [101] direction are joined into layers parallel to the (101) plane formation of Cu-Cl bonds and inter-chain hydrogen bonds. There are no hydrogen-bonding inter-actions between the layers and the three-dimensional structure of is based on the weak C-H⋯O and C-H⋯Cl contacts.
配合物[3,10-双-(3-羧基丙基)-1,3,5,8,10,12-六氮杂环十四烷-κ^6,κ^8,κ^10,κ^12]二氯合铜(II)，[CuCl(C₁₄H₂₆N₆O₄)]或[Cu(H₂O)Cl(C₁₄H₂₄N₆O₄)]（）的不对称单元由一个中心对称的大环铜(II)二价阳离子和一个氯离子组成。异金属化合物聚[[水合-[μ-3,10-双-(3-羧基丙基)-1,3,5,8,10,12-六氮杂环十四烷-κ^6,κ^8,κ^10,κ^12:κ^6':κ^6'','^6''']-μ-氯-铜(II)镉(II)]1.25水合物]，{[CuCd(C₁₄H₂₆N₆O₄)Cl(H₂O)]·1.25H₂O}或{[CuCd(C₁₄H₂₄N₆O₄)(H₂O)Cl]·(1.25H₂O)}（）的组成部分是[Cu(C₁₄H₂₄N₆O₄)(H₂O)]基团与CdCl单元、大环去质子化羧基以及四个部分占据的结晶水分子配位。在每个化合物中，Cu离子在赤道平面上通过大环配体的四个仲氮原子配位，该配体采用能量上最稳定的-III构象，并且在和中分别在四方拉长的-CuNCl和-CuN(H₂O)Cl八面体几何构型中有两个相互轴向的配体。中Cd离子的配位环境是一个由不同大环的两个双齿配位去质子化羧基和两个氯离子形成的CdO₂Cl₂扭曲八面体，其中一个氯离子在Cu和Cd离子之间起μ-桥连作用。两种配合物的扩展结构明显为层状。特别是，由于大环的羧基、氯原子和仲氨基参与的氢键相互作用，中晶体中的电中性分子沿[101]方向排列成链；链间氢键导致平行于(101)平面的层。在的晶体中，沿[101]方向的聚合物链通过形成Cu-Cl键和链间氢键连接成平行于(101)平面的层。层间没有氢键相互作用，的三维结构基于弱的C-H⋯O和C-H⋯Cl接触。
