Single crystal growth of the novel Mn2(OH)2SO3, Mn2F(OH)SO3, and Mn5(OH)4(H2O)2[SO3]2[SO4] compounds using a hydrothermal method

Abstract

The new compounds Mn₂(OH)₂SO₃, Mn₂F(OH)SO₃, and Mn₅(OH)₄(H₂O)₂[SO₃]₂[SO₄] were synthesized using a hydrothermal route and their crystal structures were determined using single crystal X-ray diffraction data. Mn₂(OH)₂SO₃ and Mn₂F(OH)SO₃ crystallized with the space group Pnma, a = 7.3580(14), b = 10.3429(20), c = 5.7611(11) Å, Z = 4; and a = 7.413(4), b = 10.139(5), c = 5.717(3) Å, Z = 4, respectively, whereas Mn₅(OH)₄(H₂O)₂[SO₃]₂[SO₄] crystallized with the space group P2₁/m, a = 7.6117(7), b = 8.5326(7), c = 10.9273(9) Å, β = 101.6005(13)°, Z = 2. Mn₂(OH)₂SO₃ and Mn₂F(OH)SO₃ consist of a 3D-framework of manganese octahedra sharing corners and edges and giving rise to 1D-tunnels along the a axis in which are located the sulfur atoms, whereas Mn₅(OH)₄(H₂O)₂[SO₃]₂[SO₄] consists of a 3D-framework of MnO₅, MnO₆, SO₃, and SO₄ polyhedra. Mn₅(OH)₄(H₂O)₂[SO₃]₂[SO₄] is the first transition metal mixed sulfate–sulfite inorganic compound. Bent and symmetrically bifurcated hydrogen bonds were observed in these materials.