Issue 40, 2021

Influence of the synthetic conditions on a formation of 1-D, 2-D and 3-D copper–chloride coordination polymers

Abstract

By means of electrochemical alternating current synthesis starting from a methanol solution of CuCl2·2H2O and dabco (dabco = 1,4-diazabicyclo[2.2.2]octane) titrated with HCl, a salt of (H2dabco)Cu2Cl4 composition (I) was obtained. It consists of infinite chains composed from vertex-sharing Cu2Cl2 rhombs and diprotonated (H2dabco)2+ cations. The use of ethanol as a solvent and a higher CuCl2·2H2O : dabco ratio lead to the formation of the (H2dabco)Cu3Cl5 (II) salt. Its inorganic part consists of infinite corrugated ribbons in which each half-loop is closed by an additional chloride bridge. The decrease of the CuCl2·2H2O : dabco ratio leads to the appearance of the compound (H2dabco)5Cu12Cl22·H2O (III), which contains unique anionic 2-D (CuI12Cl22)10− networks. Syntheses carried out in aprotic solvents led to the formation of known (H2dabco)CuCl3 salt. Recrystallization of the compound III from dymethyl sulfoxide (DMSO) unexpectedly led to the appearance of two copper(I) chloride complexes with in situ formed dymethylsulfide (DMS): the already known CuCl·DMS and observed for the first time (CuCl)7(DMS)3 (IV). The latter contains two types of infinite copper–chloride columns, consisting of cubane-like Cu4Cl4 and prismane-like Cu6Cl6 clusters. μ-Sulfur (DMS) bridges connect the above columns to form a 3-D network. Crystallisation from the initial CuCl2·2H2O – dabco – HCl mixture yielded deep-red crystals of the unknown (H2dabco)Cu2IICl6 salt (V) among other products. Its structure consists of infinite cupro(II)-chloride chains and discrete (H2dabco)2+ cations.

Graphical abstract: Influence of the synthetic conditions on a formation of 1-D, 2-D and 3-D copper–chloride coordination polymers

Supplementary files

Article information

Article type
Paper
Submitted
08 ဩ 2021
Accepted
22 စက် 2021
First published
22 စက် 2021

CrystEngComm, 2021,23, 7171-7178

Influence of the synthetic conditions on a formation of 1-D, 2-D and 3-D copper–chloride coordination polymers

E. Goreshnik, CrystEngComm, 2021, 23, 7171 DOI: 10.1039/D1CE01048D

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