Lanthanide oxyhalide

Portion of lattice of lutetium oxychloride.

A lanthanide oxyhalide is an inorganic compound that contains a lanthanide (Ln), oxide, and halide (X). The simplest members have the formula LnOX. The three heavier member of this class, lanthanide oxychlorides, lanthanide oxybromides, and lanthanide oxyiodides, can be prepared by hydrolysis of the corresponding lanthanide trihalides :

LnX3 + H2O → LnOX + 2 HX (X = Cl, Br, I)

The lanthanide oxyfluorides are the unique member of the series. They are prepared by the thermal reaction of the trifluorides and the oxides:

Ln2O3 + LnF3 → 3LnOF

Inventory

Lanthanide oxyhalide
LnOFstructure typeLnOClstructure typeLnOBrstructure typeLnOIstructure type
LaOFfluoriteLaOClPbFClLaOBrPbFClLaOI
CeOFfluoriteCeOClPbFClCeOBrPbFClCeOI
PrOFfluoritePrOClPbFClPrOBrPbFClPrOI??
NdOFfluoriteNdOClPbFClNdOBrPbFClNdOI
PmOFfluoritePmOCl??I PmOBrPmOI
SmOFfluoriteSmOClPbFClSmOBrPbFClSmOI
EuOFfluoriteEuOClPbFClEuOBrPbFClEuOI
GdOFfluoriteGdOClPbFClGdOBrPbFClGdOI
TbOFTbOClPbFClTbOBrPbFClTbOI
DyOFfluoriteDyOClPbFClDyOBrPbFClDyOI
HoOFfluoriteHoOClPbFClHoOBrPbFClHoOI
ErOFfluoriteErOCldimorphic: PbFCl & SmISErOBrPbFClErOI
TmOFfluoriteTmOClSmISTmOBrPbFClLuOI
YbOFfluoriteYbOClSmISYOBrPbFClYOI
LuOFfluoriteLuOClSmIS-typeLuOBrPbFClLuOIPbFCl

Structures

Subunit of solid LaOCl, showing the atomic structure as determined by X-ray crystallography. The larger green spheres are chloride, the tetrahedrally-bonded smaller green spheres represent oxide. This image is that of PbFCl, which has the same motif.

The lanthanide oxychlorides, oxybromides, and oxyiodides adopt layered structures featuring 8-or 9-coordinated Ln ions sandwiched between arrays of halide and oxides. Most of the lighter oxychlorides follow the PbFCl motif, but the three heaviest adopt structures like that of SmSI (samarium sulfide iodide).

The oxyfluorides adopt the fluorite structure.

References

  1. 1 2 Mayer, I.; Zolotov, S.; Kassierer, F. (1965). "The Crystal Structure of Rare Earth and Yttrium Oxybromides". Inorganic Chemistry. 4 (11): 1637–1639. doi:10.1021/ic50033a022.
  2. 1 2 3 Dabachi, Jamal; Body, Monique; Dittmer, Jens; Fayon, Franck; Legein, Christophe (2015). "Structural refinement of the RT LaOF phases by coupling powder X-Ray diffraction,19F and139La solid state NMR and DFT calculations of the NMR parameters". Dalton Transactions. 44 (47): 20675–20684. doi:10.1039/C5DT04028K. PMID 26565802.
  3. 1 2 3 4 5 6 7 8 9 10 Hölsä, Jorma; Lahtinen, Manu; Lastusaari, Mika; Valkonen, Jussi; Viljanen, Jussi (2002). "Stability of Rare-Earth Oxychloride Phases: Bond Valence Study". Journal of Solid State Chemistry. 165: 48–55. doi:10.1006/jssc.2001.9491.
  4. ↑ Zimmermann, Sina; Meyer, Gerd (2007). "Lutetium(III) oxide iodide". Acta Crystallographica Section E: Structure Reports Online. 63 (12): i193. doi:10.1107/S160053680705283X.
  5. ↑ Pasero, M.; Perchiazzi, N. (1996). "Crystal structure refinement of matlockite". Mineralogical Magazine. 60 (402): 833–836. doi:10.1180/minmag.1996.060.402.15.
  6. ↑ Savigny, N.; Laruelle, P.; Flahaut, J. (1973). "Structure cristalline du sulfoiodure de samarium, SmSI". Acta Crystallographica Section B Structural Crystallography and Crystal Chemistry. 29 (2): 345–347. doi:10.1107/S056774087300244X.