Crystal structure of three chloridocuprate(I, II) complexes with methylene blue (MB) counterions

Abstract

Abstract Three chloridocuprate complexes with methylene blue counterions of the chemical compositions [MB]+ 2[CuCl4]2− · H2O (1), [MB]+ 2[CuCl4]2− (2) and [(MB)+(CuCl2)−]3 (3) (where [MB]+ – methylthioninium cation; methylene blue cation) have been prepared by solvent-assisted mechanochemical synthesis. The reactions were carried out by mixing the copper(II) chloride dihydrate, CuCl2⋅2H2O, and methylene blue pentahydrate, [MB]+Cl− · 5H2O by grinding in an agate mortar with the addition of DMF as a solvent. The crystal structures of the compounds have been determined by single-crystal X-ray diffraction. The content of an asymmetric unit of the crystals consists of: (1) a tetrahedral [CuCl4]2− anion, two [MB]+ cations and one water molecule of crystallization; (2) a tetrahedral [CuCl4]2− anion and two [MB]+ cations; (3) trimeric [(MB)+(CuCl2)−]3 molecules with the Cu atoms coordinated by a nitrogen atom of the phenothiazine ring and two chlorine ions in a trigonal planar geometry with the copper atom in the oxidation state of +1.