A mixed-valence copper chloride coordination polymer composed of one-dimensional cationic and anionic substructures. Issue 48 (24th November 2022)

• Record Type: Journal Article
• Authors: Park, Hee Sun; Lee, Jae-Chang; Jung, Myung-Hwa; Lee, Yong-Min; Nam, Wonwoo; Hur, Nam Hwi
• Is Part Of: CrystEngComm. Volume 24:Issue 48(2022)
• Page Start: 8354
• Page End: 8362
• Publication Date: 2022-11-24
• Subjects: Crystals -- Periodicals; Crystal growth -- Periodicals; Crystallography -- Periodicals; Cristaux -- Périodiques; Cristaux -- Croissance -- Périodiques; Cristallographie -- Périodiques; 548
• DOI: 10.1039/d2ce01370c
• Languages: English
• ISSNs: 1466-8033

Abstract

Abstract : A coordination polymer composed of cationic [Cu II Cl2 (Hdatrz)2 ] 2+ and anionic [Cu I 2 Cl4 ] 2− substructures was obtained from the reaction of 3, 5-diamino-1, 2, 4-triazole (datrz) with Cu I Cl and Cu II Cl2 in the presence of HCl. Abstract : A new three-dimensional (3D) coordination polymer [{Cu II Cl2 (Hdatrz)2 }(Cu I 2 Cl4 )] n (1 ) that consists of two independent cationic and anionic substructures has been synthesized from the reaction of 3, 5-diamino-1, 2, 4-triazole (datrz) with Cu I Cl and Cu II Cl2 . The cationic subunit, [Cu II Cl2 (Hdatrz)2 ] 2+, has a one-dimensional (1D) structure based on [Cu II Cl2 (Hdatrz)2 Cl2 ] octahedral units, while the anionic component [Cu I 2 Cl4 ] 2− consists of 1D chains of edge-sharing CuCl4 tetrahedra. The cationic and anionic chains are linked through interionic hydrogen bonding. The protonated datrz ligand plays an essential role in constructing the supramolecular framework. The magnetic Cu II (d 9 ) ion occupies the octahedral center of the cationic substructure, while the non-magnetic Cu I (d 10 ) ion resides in the tetrahedral core of the anionic substructure. The temperature-dependent magnetic susceptibility of 1 reveals a typical paramagnetic behavior, and the Curie–Weiss fit shows a magnetic moment of 2.04 μ B per Cu II . There is weak antiferromagnetic ordering below a Néel temperature of 2.46 K, presumably due to an antiferromagnetic interaction between neighboring Cu II ions linked by two Cl ligands. The EPR spectra of 1 suggest that the [Cu II Cl2 (Hdatrz)2 Cl2 ] subunit has a tetragonally elongated octahedral geometry and the complex 1 contains mixed-valence Cu I and Cu II species. In addition, we discovered a novel molecular compound with a stoichiometry of (H2 datrz)Cl2 (2 ), which was prepared by the reaction of concentrated hydrochloric acid with datrz in the absence of copper chlorides. X-ray crystal structure determination shows that the compound consists of an unusual di-protonated H2 datrz 2+ cation and two charge-compensating Cl − anions.