Crystal structures of manganese hydrogen sulfates – Mn(HSO4)2, Mn(HSO4)2 · H2O and Mn(HSO4)2(H2SO4)2

Abstract

Abstract In the binary system MnSO4/H2SO4, two new acid sulfates were synthesized and their structures have been determined: Mn(HSO4)2, Mg(HSO4)2 type, P21/n, Z = 2, a = 5.014(1) Å, b = 8.426(2) Å, c = 7.452(1) Å, β = 100.05(1)°, R 1 = 0.035, and Mn(HSO4)2(H2SO4)2, Cd(HSO4)2(H2SO4)2 type, P21/c, Z = 4, a = 5.166(1) Å, b = 15.397(3) Å, c = 7.963(1) Å, β = 104.74(2)°, R 1 = 0.039. Mn(HSO4)2 · H2O was isolated from 85% sulfuric acid, Mg(HSO4)2 · H2O type, P21/n, Z = 4, a = 8.720(2) Å, b = 5.084(1) Å, c = 15.663(3) Å, β = 101.11(3)°, R 1 = 0.026. In all compounds, the manganese atoms are octahedrally coordinated by oxygen atoms originated from either HSP4 − or H2SO4 tetrahedra. Hydrogen bonding systems consist of layers or chains. In the structure of Mn(HSO4)2, the HSO4 − tetrahedra form infinite zigzag chains along [010]. The structure of Mn(HSO4)2 · H2O is characterized by layers of HSO4 − tetrahedra and H2O molecules connected by hydrogen bonds. Layers consisting of HSO4 − and H2SO4 tetrahedra are formed in the structure of Mn(HSO4)2(H2SO4)2.