Water Molecule Dispositions in the Cesium Sulfate α- and β-Alums: Single-Crystal Neutron Diffraction Studies of CsM(SO₄)₂.12H₂O (M=V, Rh)

Abstract

Room-temperature single-crystal neutron diffraction studies are recorded for two alums, Cs( Rh /V)(SO₄)₂.12H₂O [cubic, Pa3, a 12.357(5) ( Rh ), 12.434(1)Ǻ (V)], residuals 0.037 and 0.068 for 328 and 164 'observed' reflections, with the intention of defining water molecule hydrogen atom orientations. Whereas the two tervalent hexaaqua cations are similar in size [ r_{M -O} = 2.010(6)Ǻ (M = V) and 2.006(2)Ǻ (M = Rh )] the vanadium salt adopts the β alum modification while rhodium gives an α alum. Significantly, the water coordination geometry is different in the two cases with the tilt angle between the plane of the water molecule and the M-O bond vector being 1° (M = V) and 35° (M = Rh ). The tilt angle for water coordinated to rhodium in CsRh (SeO₄)₂.12H₂O is inferred from the unit cell dimensions to be similar to that of the corresponding sulfate salt and not that which generally pertains for caesium selenate alums. Significant differences in the H-O-H bond angle are found for trigonal planar and trigonal pyramidal water coordination, suggesting that differences in the metal(III)-water interaction are a determinant of the geometry of the coordinated water molecule in the caesium sulfate/ selenate alum lattices.