STRUCTURE OF ANHYDROUS TITANYL SULFATE, TITANYL SULFATE MONOHYDRATE AND PREDICTION OF A NEW STRUCTURE

(1) Titanyl sulfate, TiOSO4, M(r) = 159.96, orthorhombic, P2(1)ma, a = 10.942 (1), b = 5.158 (1), c 25.726 (2) angstrom, U = 1452.0 (3) angstrom3, D(m) (flotation) = 2.96 (2), D(x) = 2.93 (1) g cm-1, Z = 16, lambda(Mo Kalpha) 0.7107 angstrom, mu = 23.46 cm-1 F(000) = 1248, T = 293 K, final R = 0.168 for 2333 counter reflections. A combined X-ray and transmission electron microscopy study allowed the determination and refinement of this structure on a supercell of WPO3 (a and b equal those above but c is 4 x c). The structure consists of an infinite array of corner-shared octahedra and tetrahedra and Ti-O distances range from 1.70 (2) to 2.05 (1) angstrom. (2) Titanyl sulfate monohydrate, TiOSO4.H2O, M(r) = 177.97, orthorhombic, P2(1)2(1)2(1), a = 9.818 (1), b = 5.133 (1), c = 8.614 (2) angstrom, U = 434.1 (2) angstrom3, Z = 4, D(m) (flotation) = 2.71 (1), D(x) = 2.72 (1) g xm-3, lambda(Mo Kalpha) = 0.7107 angstrom, mu = 23.46 cm-1, F(000) = 352, T = 293K, final R = 0.0190 for 1985 counter reflections. The structure consists of [TiO]n2n+ chains parallel to the crystallographic b axis linked by sulfate tetrahedra to form the three-dimensional structure. The titanyl bridge is asymmetric [1.6870(9) and 1.9641 (8)angstrom] and Ti-O distances range from 1.687 to 2.136 angstrom. A new structure derived from that of titanyl sulfate hydrate is predicted.