Nuclear and magnetic structures and magnetic properties of synthetic brochantite, Cu4(OH)6SO4

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Abstract
Cu4(OH)6SO4 (1) and Cu4(OD)6SO4 (2) were obtained by hydrothermal syntheses from copper sulfate and sodium hydroxide in H2O and D2O, respectively. They crystallize in the monoclinic system, space group P21/a (14), a = 13.1206(5), b = 9.8551(3), c = 6.0295(2) Å, β = 103.432(3)°, V = 758.3(1) Å3, Z = 4 and a = 13.1187(5), b = 9.8552(3), c = 6.0293(2) Å, β = 103.410(3)°, V = 758.3(1) Å3, Z = 4, respectively. They are iso-structural to the mineral brochantite and consist of double chains of edge-sharing copper octahedra that are connected to one another by corners to form corrugated planes along bc; these planes are in-turn bridged by the unprecedented µ7-sulfate tetrahedra to give a 3D-structure. All the hydrogen atoms were precisely located from refinement of the neutron powder diffraction data of the deuterated sample. Magnetic susceptibility data reveal a low-dimensional behavior at high temperature and the presence of both ferromagnetic and antiferromagnetic super-exchanges resulting in a 3D long-range antiferromagnetic ordering at 7.5 K accompanied by a small canting of the moments. The transition is confirmed by a λ-peak in the specific heat. The magnetic structure at 1.4 K shows the moments are oriented perpendicular to the corrugated planes with alternation along ±a for neighboring chains within the double chains. The enhanced incoherent scattering at low-angle suggests the existence of short-range ferromagnetic clusters.

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