- Email: [email protected]
Dioxane addition compounds of hydrated yttrium, lanthanum and rare earth perchlorates
J.ImxZ.NuCt.Ctnm.,t~k%VoL~kpp. t~t to D53. l~rSsm~PmnLtd, l~ist~mllqt~t
DIOXANE ADDITION COMPOUNDS OF HYDRATED YTTRIUM, LANTHANUM AND RARE EARTH PERCHLORATES G. VlCEm'lm, J. V. VALARELU,M. Pmu~m and E. GmsBm~Cm" Departmento de Qufmica • Depa~tmento de Mineralo#a da Facu]dade de Filosofm, C~encias • Letras da Universidade de Sgo Paulo, Brazil (Recelved 5 February 1962;/n revisedform 3 April 1962)
IN a previous communication(1) the preparation of addition compounds between dioxane and yttrium, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium and erbium hydrated perchlorates were reported. It was observed that the thullium, dysprosium, holmium, terbium, ytterbium and lutetium hydrated perchlorates react with dioxane in the same way as the others, forming compounds with the general formula M(CIO4)3"9H20"4C4HsO2. This note describes the preparation of these compounds together with infra-red data and some isomourphous relations observed by X-ray powder patterns. Infra-red spectra. The Spectra of the yttrium, lanthanum and rare earth c o m p l a perchlorates where determined in the infra-red region. In all cases, the dioxane spectrum was observed without essential modification. The peaks at 875 and 1122 c m - m ) appeared in the infra-red spectra of all substances. According to results obtained with similar substances described in previous paperso, 4) the binding with dioxane must be relatively weak. X-ray powder patterns. The X-ray powder procedure showed two series of isomorphous substances: (a) The first one includes the corresponding yttrium, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium and dysprosium compounds. Co) The second one includes the corresponding holmium, thullium, erbium, ytterbium and lutetium compounds. The X-ray diffraction data will be published elsewhere. EXPERIMENTAL a. Dioxane addition eompoum/a. They were prepared by hoating on a water bath the corrmponding oxidm (Tb4OT, Dy~K)s, HoaO3, TmaO3, Yb203 and Lu203, reagent grade, Johnson, Matthcy E. Co., London) with tim appropriate amount of 70 per cent pttchloric tmid and a few drops of perhydrol addod. Tim solutions weft evaporatod to near dryness, tim residues ground with ¢~tss dioxatm and the resulting crystals recrystallimd from hot dioxane. All compounds were stored in a vacuum dmiccator over calcium chloride. (t) G. VicmqnNl, M. Pmuulm and E. OIESmum~, Ber. Dtsch. Chem. Ges. 94, 1153 (1961). (2) S. C. Btmm~ and R. M. BAnOBIt,J. Amer. Chem. $oe. 72, 4397 (1950). (3) M. Ptmmm(, E. Gmsmm~r, W. O. R. & COum~Rooand (3. VICtmlNt, Ber. Dtsch. Chem. Oes. 95, 257 (1962). (4) B. ~ , W. O. R. de CAMAaOO,G. Vtc~rnm and M. lhnmnm, J. Is~rt. N~I. Chem. 24, 381 (1962). 1351
1352
O. Vlc~ter~, .l.V. V ~ m ~ t ~ , M. l~m~.~ and E. O I ~ E C . T
O
°
8
O
8
i
.oo~ o .It
Dioxane adchTloncompounds of hydrated yttrium, lanthanum and rare earth perc~dorates 1353 b. Analytical data. The rare earths were determined by the usual oxalate method. Water and perchlorat~ were determined by methods described in a previous paper.CS) The analytical results arc summarized in Table 1. c. Solubilities. All compounds are very soluble in water, methanol, ethanol, acetone and ethylacetat¢. They are practically insoluble in chloroform carbon tetrachloride and benzene. All compounds are moderately soluble in hot dioxane and could bc recrystallized from this solvent. d. Infra-red spectra. The infra-red spectra were obtained with a Perkin-Elmcr Model 137 Double Beam Recording Spectrophotometer, using Nujol suspensions between rock salt plates, e. X-ray diffraction patterns. They were obtained with a NORELCO unit, Buerger powder camera (114.6 mm). All samples were sealed in 0.5 mm Lindemann glass capillartubes and exposed to Cu-Ka radiation (A = 1-5148 A) at room temperature, during 18--24 hr. Acknowledgements--The authors wish to thank the Rockefeller Foundation and Conselho Nacional de Pesquisas (Rio de Janeiro) for financial support. ~5~G. VlcBbrr~i, M. PmutmR, W. G. R. de CAMAROOand J. M. V. COUTI~HO, Ber. DtscA. Chem. Ges. 94, 1063 (1961).
DIOXANE ADDITION COMPOUNDS OF HYDRATED YTTRIUM, LANTHANUM AND RARE EARTH PERCHLORATES G. VlCEm'lm, J. V. VALARELU,M. Pmu~m and E. GmsBm~Cm" Departmento de Qufmica • Depa~tmento de Mineralo#a da Facu]dade de Filosofm, C~encias • Letras da Universidade de Sgo Paulo, Brazil (Recelved 5 February 1962;/n revisedform 3 April 1962)
IN a previous communication(1) the preparation of addition compounds between dioxane and yttrium, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium and erbium hydrated perchlorates were reported. It was observed that the thullium, dysprosium, holmium, terbium, ytterbium and lutetium hydrated perchlorates react with dioxane in the same way as the others, forming compounds with the general formula M(CIO4)3"9H20"4C4HsO2. This note describes the preparation of these compounds together with infra-red data and some isomourphous relations observed by X-ray powder patterns. Infra-red spectra. The Spectra of the yttrium, lanthanum and rare earth c o m p l a perchlorates where determined in the infra-red region. In all cases, the dioxane spectrum was observed without essential modification. The peaks at 875 and 1122 c m - m ) appeared in the infra-red spectra of all substances. According to results obtained with similar substances described in previous paperso, 4) the binding with dioxane must be relatively weak. X-ray powder patterns. The X-ray powder procedure showed two series of isomorphous substances: (a) The first one includes the corresponding yttrium, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium and dysprosium compounds. Co) The second one includes the corresponding holmium, thullium, erbium, ytterbium and lutetium compounds. The X-ray diffraction data will be published elsewhere. EXPERIMENTAL a. Dioxane addition eompoum/a. They were prepared by hoating on a water bath the corrmponding oxidm (Tb4OT, Dy~K)s, HoaO3, TmaO3, Yb203 and Lu203, reagent grade, Johnson, Matthcy E. Co., London) with tim appropriate amount of 70 per cent pttchloric tmid and a few drops of perhydrol addod. Tim solutions weft evaporatod to near dryness, tim residues ground with ¢~tss dioxatm and the resulting crystals recrystallimd from hot dioxane. All compounds were stored in a vacuum dmiccator over calcium chloride. (t) G. VicmqnNl, M. Pmuulm and E. OIESmum~, Ber. Dtsch. Chem. Ges. 94, 1153 (1961). (2) S. C. Btmm~ and R. M. BAnOBIt,J. Amer. Chem. $oe. 72, 4397 (1950). (3) M. Ptmmm(, E. Gmsmm~r, W. O. R. & COum~Rooand (3. VICtmlNt, Ber. Dtsch. Chem. Oes. 95, 257 (1962). (4) B. ~ , W. O. R. de CAMAaOO,G. Vtc~rnm and M. lhnmnm, J. Is~rt. N~I. Chem. 24, 381 (1962). 1351
1352
O. Vlc~ter~, .l.V. V ~ m ~ t ~ , M. l~m~.~ and E. O I ~ E C . T
O
°
8
O
8
i
.oo~ o .It
Dioxane adchTloncompounds of hydrated yttrium, lanthanum and rare earth perc~dorates 1353 b. Analytical data. The rare earths were determined by the usual oxalate method. Water and perchlorat~ were determined by methods described in a previous paper.CS) The analytical results arc summarized in Table 1. c. Solubilities. All compounds are very soluble in water, methanol, ethanol, acetone and ethylacetat¢. They are practically insoluble in chloroform carbon tetrachloride and benzene. All compounds are moderately soluble in hot dioxane and could bc recrystallized from this solvent. d. Infra-red spectra. The infra-red spectra were obtained with a Perkin-Elmcr Model 137 Double Beam Recording Spectrophotometer, using Nujol suspensions between rock salt plates, e. X-ray diffraction patterns. They were obtained with a NORELCO unit, Buerger powder camera (114.6 mm). All samples were sealed in 0.5 mm Lindemann glass capillartubes and exposed to Cu-Ka radiation (A = 1-5148 A) at room temperature, during 18--24 hr. Acknowledgements--The authors wish to thank the Rockefeller Foundation and Conselho Nacional de Pesquisas (Rio de Janeiro) for financial support. ~5~G. VlcBbrr~i, M. PmutmR, W. G. R. de CAMAROOand J. M. V. COUTI~HO, Ber. DtscA. Chem. Ges. 94, 1063 (1961).