Synthesis, crystal structure, and thermodynamic properties of two new selenate chlorides: M2Cu(SeO4)Cl2 with M = K and Rb

Abstract

Two new selenate chlorides have been prepared for the first time by hydrothermal method. Their crystal structures have been determined. Both compounds are related to the chlorothionite mineral structure type but not isostructural to each other. K2Cu(SeO4)Cl2 crystallize in the orthorhombic system with the space group Pnma (#62) and unit cell parameters a = 7.7941(2)Å, b = 6.1297(2) Å, c = 16.6644(5) Å, V = 796.15(4) Å3, Z = 4 whereas Rb2Cu(SeO4)Cl2 crystallize in monoclinic system, P21/n (#14), and parameters a = 8.0701(3), b = 12.9474(5), c = 16.9354(7), β = 103.657(2)°, V = 1719.49(12) Å3, Z = 8. Potassium compound are isostructural to the related sulfate chloride, while rubidium selenate is differ from their sulfate analogue and from prototype compound K2Cu(SO4)Cl2. Both examined crystal structures feature copper ions in planar coordination CuO2Cl2 which form isolated magnetic chains along ⟨0 1 0⟩ direction in the structure. The study of M2Cu(SeO4)Cl2 was carried out in measurements of magnetic susceptibility χ(T) = M/B in the temperature range 2–350 K, magnetization M(B) at 2 K and specific heat Cp(T) in the range 2–120 K. At lowering temperature, the magnetic susceptibility exhibits no anomalies and follows by Curie law. An increase of the Cp(T) curve below 3 ÷ 8 K indicates the release of magnetic entropy. The study of thermodynamic properties unexpectedly shows that the investigated selenates M2Cu(SeO4)Cl2 (M = K and Rb) behave like paramagnets and the interaction between copper ions in the structural chains is negligible, opposite related sulfates demonstrating 1D magnetic behavior for Cu2+ magnetic ions.