Crystal structure, spectroscopic properties, and magnetic behavior of the fluoride-derivatized lanthanoid(III) ortho-oxomolybdates(VI) LnF[MoO 4] ( Ln=Sm–Tm)

The fluoride-derivatized lanthanoid(III) ortho-oxomolybdates(VI) LnF[MoO 4] ( Ln=Sm–Tm) crystallize in the monoclinic space group P2 1/ c with four formula units per unit cell ( a=516–528 pm, b=1220–1248 pm, c=659–678 pm, β=112.5–113.1°). The structure contains one crystallographically unique Ln 3+...

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Bibliographic Details
Published in:	Journal of solid state chemistry 2008-10, Vol.181 (10), p.2828-2836
Main Authors:	Hartenbach, Ingo, Strobel, Sabine, Dorhout, Peter K., Schleid, Thomas
Format:	Article
Language:	eng
Subjects:	ANIONS ARSENIC CATIONS Condensed matter: structure, mechanical and thermal properties Crystal structures DERIVATIZATION Exact sciences and technology FLUORIDES FLUORINE IONS Inorganic compounds INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY Lanthanoids LAYERS Magnetic measurements MOLYBDATES MOLYBDENUM IONS MONOCLINIC LATTICES OXIDES Oxomolybdates Physics RARE EARTH COMPOUNDS SPACE GROUPS SPECTROSCOPY Structure of solids and liquids crystallography Structure of specific crystalline solids
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Summary:	The fluoride-derivatized lanthanoid(III) ortho-oxomolybdates(VI) LnF[MoO 4] ( Ln=Sm–Tm) crystallize in the monoclinic space group P2 1/ c with four formula units per unit cell ( a=516–528 pm, b=1220–1248 pm, c=659–678 pm, β=112.5–113.1°). The structure contains one crystallographically unique Ln 3+ cation surrounded by two fluoride and six oxide anions in a square antiprism (CN=8). The square antiprisms [ LnF 2O 6] are interconnected via three edges to form layers ∞ 2 { [ Ln F 2 / 2 e O 4 / 2 e O 2 / 1 t ] 6 - } parallel (010), which are cross-linked along [010] by Mo 6+ in tetrahedral oxygen coordination to form the three-dimensional crystal structure. The fluoride anions within this arrangement exhibit a twofold coordination of Ln 3+ cations in the shape of a boomerang, which is connected to another F − anion to form planar [F 2 Ln 2] 4+ rhombuses. Magnetic measurements for GdF[MoO 4], TbF[MoO 4], and DyF[MoO 4] show Curie–Weiss behavior, despite the peculiar arrangement of the lanthanoid(III) cations in layers comparable with those of gray arsenic. Furthermore, Raman, infrared, and diffuse reflectance spectroscopy data for these compounds were recorded and interpreted. View at the crystal structure of LnF[MoO 4] ( Ln=Sm–Tm) along [100] with special emphasis on the isolated [MoO 4] 2− tetrahedra ( blue) and the [F 2 Ln 2] 4+ rhombuses ( green).
ISSN:	0022-4596 1095-726X