Abstract <p>Copper(II) and cobalt(II) halide complexes (H<sub>2</sub>L)[CuCl<sub>4</sub>]⋅H<sub>2</sub>O (<b>I</b>), (HL)<sub><i>n</i></sub>[CuCl<sub>3</sub>]<sub><i>n</i></sub> (<b>II</b>), (H<sub>2</sub>L)[CoCl<sub>4</sub>]⋅(H<sub>2</sub>L)Cl<sub>2</sub>⋅<i>x</i>H<sub>2</sub>O (where <i>x</i> = 1.5 (<b>III</b>) or 2 (single crystal)) and (HL)[Cu(H<sub>2</sub>O)Br<sub>3</sub>] (<b>IV</b>), L is 1‑(4-chlorophenyl)piperazine were synthesized. Two different [CuCl<sub>4</sub>]<sup>2–</sup> anions were found in the structure of <b>I</b>, which are bound to organic cations and crystal water molecules by a network of hydrogen bonds. In compound <b>II</b>, the [CuCl<sub>3</sub>]<sup>–</sup> anion is completed to a distorted square pyramid, forming polymer chains. Compound <b>III</b> is a mixed salt with the tetrahedral anion [CoCl<sub>4</sub>]<sup>2–</sup>. Thermal analysis data&#xa0;show&#xa0;that compound <b>I</b> loses water (~70°C) and&#xa0;HCl&#xa0;(~158°C); melting&#xa0;and subsequent decomposition&#xa0;occurs&#xa0;at&#xa0;178°C. Compound <b>II</b> exhibits&#xa0;incongruent&#xa0;melting&#xa0;at&#xa0;178°C&#xa0;with&#xa0;transition to the exothermic stage of destruction. The similarity of the thermal behavior of <b>I</b> and <b>II</b> at 178°C indicates the formation of <b>II</b> after the removal of volatile components from compound <b>I</b>. Complex <b>III</b> is thermally resistant to 70°C, with a total mass loss of 20% to 300°C corresponding to the removal of all water molecules and 3 HCl per formula unit. Compound <b>IV</b> melts above 80°C without loss of mass, decomposition is observed when heated above 150°C.</p>

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Syntheses, Structures, and Properties of Copper(II) and Cobalt(II) Complexes with 1-(4-Chlorophenyl)Piperazinium Cations

  • A. N. Protsenko,
  • O. G. Shakirova,
  • N. V. Kuratieva,
  • A. E. Protsenko

摘要

Abstract

Copper(II) and cobalt(II) halide complexes (H2L)[CuCl4]⋅H2O (I), (HL)n[CuCl3]n (II), (H2L)[CoCl4]⋅(H2L)Cl2xH2O (where x = 1.5 (III) or 2 (single crystal)) and (HL)[Cu(H2O)Br3] (IV), L is 1‑(4-chlorophenyl)piperazine were synthesized. Two different [CuCl4]2– anions were found in the structure of I, which are bound to organic cations and crystal water molecules by a network of hydrogen bonds. In compound II, the [CuCl3] anion is completed to a distorted square pyramid, forming polymer chains. Compound III is a mixed salt with the tetrahedral anion [CoCl4]2–. Thermal analysis data show that compound I loses water (~70°C) and HCl (~158°C); melting and subsequent decomposition occurs at 178°C. Compound II exhibits incongruent melting at 178°C with transition to the exothermic stage of destruction. The similarity of the thermal behavior of I and II at 178°C indicates the formation of II after the removal of volatile components from compound I. Complex III is thermally resistant to 70°C, with a total mass loss of 20% to 300°C corresponding to the removal of all water molecules and 3 HCl per formula unit. Compound IV melts above 80°C without loss of mass, decomposition is observed when heated above 150°C.