Thermal decomposition behavior of the rare-earth ammonium sulfate R2(SO4)3·(NH4)2SO4

Rare-earth ammonium sulfate octahydrates of R₂(SO₄)₃·(NH₄)₂SO₄·8H₂O (R=Pr, Nd, Sm, and Eu) were synthesized by a wet process, and the stable temperature region for the anhydrous R₂(SO₄)₃·(NH₄)₂SO₄ form was clarified by thermogravimetry/differential thermal analysis, infrared, Raman, and electrical conductivity measurements. Detailed characterization of these double salts demonstrated that the thermal stability of anhydrous R₂(SO₄)₃·(NH₄)₂SO₄ is different between the Pr, Nd salts and the Sm, Eu salts, and the thermal decomposition behavior of these salts was quite different from the previous reports.     

Syntheses, crystal structures and optical spectroscopy of Ln2(SO4)3·8H2O (Ln=Ho, Tm) and Pr2(SO4)3·4H2O

The lanthanide sulphate octahydrates Ln₂(SO₄)₃·8H₂O (Ln=Ho, Tm) and the respective tetrahydrate Pr₂(SO₄)₃·4H₂O were obtained by evaporation of aqueous reaction mixtures of trivalent rare earth oxides and sulphuric acid at 300 K. Ln₂(SO₄)₃·8H₂O (Ln=Ho, Tm) crystallise in space group C2/c (Z=4, a_Ho=13.4421(4) Å, b_Ho=6.6745(2) Å, c_Ho=18.1642(5) Å, β_Ho=102.006(1) Å³ and a_Tm=13.4118(14) Å, b_Tm=6.6402(6) Å, c_Tm=18.1040(16) Å, β_Tm=101.980(8) Å³), Pr₂(SO₄)₃·4H₂O adopts space group P2₁/n (a=13.051(3) Å, b=7.2047(14) Å, c=13.316(3) Å, β=92.55(3) Å³). The vibrational and optical spectra of Ho₂(SO₄)₃·8H₂O and Pr₂(SO₄)₃·4H₂O are also reported.     

Synthesis and characterisation of TlLn(SO4)2·xH2O (Ln=La-Tb)

The compounds TlLn(SO₄)₂·2H₂OLn=La, Ce, Pr, Nd and Tl[Ln(SO₄)₂(H₂O)₃]·H₂OLn=Nd, Sm, Eu, Gd, Tb have been isolated from aqueous solutions of the corresponding sulfates. The dihydrates are all isomorphous and crystallize monoclinic, space groupP2₁/n,Z=4. The compounds which belong to the second type are also isomorphous and crystallize in monoclinic space groupP 2₁/c withZ=4.The dehydration has been studied by thermogravimetry, differential scanning calorimetry and isothermal weight change determination. The dihydrates dehydrate in a single step. For the tetrahydrates the reaction is more complex, however no intermediate phases could be isolated.The unit cell parameters, the dehydration temperatures and the dehydration enthalpies are correlated to the ionic radii ofLn ³⁺.

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Synthese und Charakterisierung von TlLn(SO₄)₂·xH₂O (Ln=La-Tb)

Zusammenfassung Die Verbindungen TlLn(SO₄)₂·2H₂OLn=La, Ce, Pr, Nd und Tl[Ln(SO₄)₂(H₂O)₃]·H₂OLn=Nd, Sm, Eu, Gd, Tb wurden aus wäßrigen Lösungen der entsprechenden Sulfate isoliert. Die Dihydrate sind alle isomorph und kristallisieren monoklin, RaumgruppeP 2₁/n,Z=4. Die Verbindungen des zweiten Typs sind auch isomorph und kristallisieren in der monoklinen RaumgruppeP 2₁/c mitZ=4.Die Dehydration wurde mit TG, DSC und dem isothermalen Gewichtsverlust untersucht. Die Entwässerung der Dihydrate verläuft in einer Stufe, die von Tetrahydraten aber in mehreren Stufen mit keiner isolierbaren Zwischenphase.Die Gitterkonstanten, die Dehydratations-Temperaturen und -Enthalpien wurden mit den Ionenradien vonLn ³⁺ korreliert.

     

Über die Auflösung der Seltenerdoxide in methanolischen Ammoniumacetatlösungen und die Darstellung von Verbindungen des TypsLn(OAc)3. 3NH4OAc. 1H2O bzw.Ln)OAc)3. 1 NH4OAc. 1H2O

Zusammenfassung Die Oxide der Lanthanide und des Yttriums lösen sich beim Erhitzen in methanol. Ammoniumacetatlösungen. Aus den Lösungen konnten Verbindungen vom TypLn(OAc)₃·3 NH₄ OAc· ·1 H₂O (Ln=La, Ce, Pr, Nd, Sm Eu, Gd, Tb, Dy, Ho) bzw. Ln(OAc)₃ 1 NH₄OAc 1 H₂O (Ln=Er, Yb, Y) isoliert werden.Die höheren Oxide PrO_1,83 und TbO_1,75 lösen sich nur unvollständig unter Valenzdisproportionierung. Der Löserückstand besteht aus PrO₂ bzw. TbO₂.

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The oxides of the lanthanides and yttrium are dissolved in the heat by methanolic ammonium acetate solutions. From the obtained solutions compounds of the typeLn(OAc)₃·3 NH₄ OAc· ·1 H₂O (Ln=La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho) andLn(OAc)₃·1 NH₄OAc·1 H₂O (Ln=Er, Yb, Y), respectively, could be isolated.The higher oxides PrO_1,83 and TbO_1,75 react incompletely and disproportionation of valence is observed. The residues consist of PrO₂ and TbO₂, respectively. *** DIRECT SUPPORT *** A3615112 00028

     

A series of 2D lanthanide (III) coordination polymers constructed from 2-(pyridin-3-yl)-1H-imidazole-4,5-dicarboxylate

Reactions of 2-(pyridine-3-yl)-1H-4,5-imidazoledicarboxylic acid (H₃PyIDC) with a series of Ln(III) ions affords ten coordination polymers, namely, {[Ln(H₂PyIDC)(HPyIDC)(H₂O)₂]·H₂O}_n [Ln=Nd (1), Sm (2), Eu (3) and Gd (4)], {[Ln(HPyIDC)(H₂O)₃]·(H₂PyIDC)·H₂O}_n [Ln=Gd (5), Tb (6), Dy (7), Ho (8) and Er (9)], and {[Y₂(HPyIDC)₂(H₂O)₅]·(bpy)·(NO₃)₂·3H₂O}_n (10) (bpy=4,4′-bipyridine). They exhibit three types of networks: complexes 1-4 are isomorphous coordination networks containing neutral 2D metal-organic layers, while complexes 5-9 are isomorphous, which consist of cationic metal-organic layers and anionic organic layers, and complex 10 is a 2D network built up from 4-connected HPyIDC²⁻ anion and 4-connected Y(III) ions. In addition, thermogravimetric analyses and solid-state luminescent properties of the selected complexes are investigated. They exhibit intense, characteristic emissions in the visible region at room temperature.     

Crystal structures of lanthanide and zirconium phosphates with general formula Ln0.33Zr2(PO4)3, where Ln=Ce, Eu, Yb

Crystal structures of synthetic phosphates Ce_0.33Zr₂(PO₄)₃, Eu_0.33Zr₂(PO₄)₃ and Yb_0.33Zr₂(PO₄)₃ have been refined by Rietveld method using powder diffraction data. Unit cell parameters: a=8.7419 (4), c=23.128 (2) Å; a=8.7659 (1), c=22.822 (1) Å; a=8.8078 (4), c=22.485 (3) Å, respectively; Z=6. Values of final R-factors in isotropic approximation: R_wp=4.00, R_wp=3.33, R_wp=4.12%, respectively. New space group P3¯c has been established for the compounds with general formula Ln_0.33Zr₂(PO₄)₃, where Ln=Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu and Y. It has been confirmed that the synthetic phosphates with general formula Ln_0.33Zr₂(PO₄)₃ belong to the NZP (sodium zirconium phosphate) structure type.     

Complex compounds of 2,2′-bipyridyl with some rare-earth bromides

The preparation of a series of new compoundsLnBr₃(2-bipy)₂·6H₂O (Ln=La, Pr, Nd, Eu, Gd) andLnBr₂OH(2-bipy)₂·4H₂O (Ln=Pr, Nd, Sm, Eu, Gd) is described. The IR spectra of these compounds are discussed. The thermal decomposition of compoundsLnBr₃(2-bipy)₂·6H₂O has been investigated.

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2,2-Bipyridylkomplexe einiger Seltenerdmetallbromide

Zusammenfassung Es wurden 2,2-Bipyridylkomplexe des TypsLnBr₃(2-bipy)₂·6H₂O (Ln=La, Pr, Nd, Sm, Eu, Gd) undLnBr₂OH(2-bipy)₂·4H₂O (Ln=Pr, Nd, Sm, Eu, Gd) dargestellt. Die IR-Spektren werden diskutiert. Die thermische Zersetzung von VerbindungenLnBr₃(2-bipy)₂·6H₂O wird untersucht.

     

4,4′-Dipyridyl and 2,2′-dipyridyl complexes of rare-earth perchlorates

4,4-Dipyridyl and 2,2-dipyridyl complexes of rare-earth perchlorates of the formulaLn(4-dipy)₈(ClO₄)₃HClO₄ · 4H₂O (Ln=La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb, Lu, Y, 4-dipy=4,4-dipyridyl) andLn(2-dipy)₃(ClO₄)₃ · 6H₂O (Ln=Pr, Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb, Lu, Y, 2-dipy = 2,2-dipyridyl) have been synthesized. The IR spectra of these compounds and other physical properties are discussed.

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4,4-Dipyridyl- und 2,2-Dipyridylkomplexe von Seltenerdmetallperchloraten

Zusammenfassung Es wurden 4,4-Dipyridylkomplexe des TypsLn(4-dipy)₈(ClO₄)₃HClO₄ · · 4 H₂O mitLn=La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb, Lu, Y und 2,2-Dipyridylkomplexe des TypsLn(2-dipy)₃(ClO₄)₃ · 6 H₂O mitLn=Pr, Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb, Lu und Y dargestellt. Die IR-Spektren und andere physikalische Eigenschaften werden diskutiert.

     

Preparation, spectroscopic properties of 1,4-di (N,N-diisopropylacetamido)-2,3(1H,4H)-quinoxalinedione (L) lanthanide complexes and the supramolecular structure of [Nd2L2(NO3)6(H2O)2]·H2O

The reaction of lanthanide nitrate with 1,4-di (N,N-diisopropylacetamido)-2,3(1H,4H)-quinoxalinedione (L) yields six novel Ln(III) complexes ([Ln₂L₂(NO₃)₆(H₂O)₂]·H₂O) which are characterized by elemental analysis, thermogravimetric analysis (TGA), conductivity measurements, IR, electronic and ¹H NMR spectroscopies. A new quinoxalinedione-based ligand is used as antenna ligand to sensitize the emission of lanthanide cations. The lowest triplet state energy level of the ligand in the nitrate complex matches better to the resonance level of Eu(III) and Sm(III) than Tb(III) and Dy(III) ion. The f-f fluorescence is induced in the Eu³⁺ and Sm³⁺ complexes by exciting into the π-π* absorptions of the ligand in the UV. Furthermore, the crystal structures of a novel binuclear complex [Nd₂L₂(NO₃)₆(H₂O)₂]·H₂O has been determined by single-crystal X-ray diffraction. The binuclear [Nd₂L₂(NO₃)₆(H₂O)₂]·H₂O complex units are linked by the intermolecular hydrogen bonds and π-π interactions to form a two-dimensional (2-D) layer supramolecule.     

Nitratkomplexe der Seltenerdelemente mit 2,2′-Bipyridin-N,N′-dioxid

Compounds ScL ₂(NO₃)₃·2 H₂O,LnL ₂(NO₃)₃·H₂O (Ln=Pr, Sm, Eu, Gd, Tb),LnL ₂(NO₃)₃·3 H₂O (Ln=Nd, Dy, Ho, Er),LnL ₃(NO₃)₃ (Ln=Pr, Nd) andLnL ₃(NO₃)₃· ·3 H₂O (Ln=Sc, Sm, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu) were isolated. They were investigated by means of thermoanalysis, IR spectroscopy, X-ray diffraction and molar conductivity.

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L=2,2-Bipyridin-N,N-dioxid=bpyO₂=C₁₀H₈N₂O₂.     

On the Lanthanide Ferrocyanides KLnFe(II)(CN)6·xH2O (Ln=La-Lu): Characterization and Thermal Evolution

The properties of a series of lanthanide hexacyanoferrate(II) n-hydrates were studied by thermal analysis, IR spectroscopy and X-ray diffraction. Thermal analysis results show that there are three kinds of complexes in this series, KLn[Fe(CN)₆]·4 H₂O (Ln=La-Nd), KSm[Fe(CN)₆]·3H₂O and KLn[Fe (CN)₆]·3.5H₂O (Ln=Eu-Lu). On the basis of IR spectra, only two different types of complexes show obvious differences. Indeed for the tetrahydrates, there is one OH stretching band; on the other hand, for the samarium phase and the 3.5 hydrates a splitting of HOH stretching mode is observed. The splitting of the H₂O band is correlated to a symmetry modification. The crystal structures of the three complexes KLn[Fe(CN)₆]·3.5H₂O (Ln=Eu, Er and Lu) were determined; they belong to orthorhombic symmetry (space group Cmcm). Heat-treated powders have been investigated by X-ray analysis which show the formation of thin needles of LnFeO₃ at 600°C.     

Rapid synthesis of ultrafine K2Ln2Ti3O10 (Ln=La, Nd, Sm, Gd, Dy) series and its photoactivity

Ultrafine-layered lanthanon titanates K₂Ln₂Ti₃O₁₀ (Ln=La, Nd, Sm, Gd, Dy) were fabricated at relatively low temperature by a stearic acid method (SAM). The obtained products were characterized by FT-IR, X-ray diffractometer, DTA-TG, scanning electron microscopy, transmission electron microscopy and BET experiments. The photocatalytic activity of the obtained products was studied and was compared with that of solid-state reaction (SSR) using photodecomposition of methyl orange as the model system. Results showed that by using SAM, the fabricating temperature was lowered (from 1100 to 800 °C) and the reacting time was shortened (from at least 11-2 h). Comparing with the product of traditional SSR, the particle size of K₂Ln₂Ti₃O₁₀ synthesized by SAM is smaller, BET surface area is higher (more than 16.97 m²/g), and photoreactivity is better. It was very interesting to find the difference in d(002) of obtained K₂Ln₂Ti₃O₁₀ for Ln=La, Nd, Sm, Gd, Dy separately and the photoactivity of K₂Ln₂Ti₃O₁₀ is strongly dependent on lanthanide, increasing in the sequence of La<Sm<Nd<Gd <Dy. A possible reason was put forward.     

N,N′-bis(salicylidene)propane-1,2-diamine lanthanide(III) coordination polymers: Synthesis, crystal structure and luminescence properties

Reaction of Ln(NO₃)₃·6H₂O with H₂L [H₂L=N,N′-bis(salicylidene)propane-1,2-diamine] gives rise to five new coordination polymers, viz. [Pr(H₂L)(NO₃)₃(MeOH)]_n (1) and [Ln(H₂L)_1.5(NO₃)₃]_n [Ln=La (2), Eu (3), Sm (4) and Gd (5)]. Crystal structural analysis reveals that H₂L effectively functions as a bridging ligand forming one-dimensional (1D) chain and two-dimensional (2D) open-framework polymers. Solid-state fluorescence spectra of 3 and 4 exhibit typical red fluorescence of Eu(III) and Sm(III) ions at room temperature while 2 emits blue fluorescence of ligand H₂L. The lowest triplet level of ligand H₂L was calculated on the basis of the phosphorescence spectrum of 5. The energy transfer mechanisms in the lanthanide polymers were described and discussed.     

The crystal structure of the monohydrate R2Mo6O21·H2O (R=Pr, Nd, Sm, and Eu): a layer structure containing disordered [Mo2O7] groups

Although R₂O₃:MoO₃=1:6 (R=rare earth) compounds are known in the R₂O₃-MoO₃ phase diagrams since a long time, no structural characterization has been achieved because a conventional solid-state reaction yields powder samples. We obtained single crystals of R₂Mo₆O₂₁·H₂O (R=Pr, Nd, Sm, and Eu) by thermal decomposition of [R₂(H₂O)₁₂Mo₈O₂₇]·nH₂O at around 685-715 °C for 2 h, and determined their crystal structures. The simulated XRD patterns of R₂Mo₆O₂₁·H₂O were consistent with those of previously reported R₂O₃:MoO₃=1:6 compounds. All R₂Mo₆O₂₁·H₂O compounds crystallize isostructurally in tetragonal, P4/ncc (No. 130), a=8.9962(5), 8.9689(6), 8.9207(4), and 8.875(2) Å; c=26.521(2), 26.519(2), 26.304(2), and 26.15(1) Å; Z=4; R₁=0.026, 0.024, 0.024, and 0.021, for R=Pr, Nd, Sm, and Eu, respectively. The crystal structure of R₂Mo₆O₂₁·H₂O consists of two [Mo₂O₇]²⁻-containing layers (A and B layers) and two interstitial R(1)³⁺ and R(2)³⁺ cations. Each [Mo₂O₇]²⁻ group is composed of two corner-sharing [MoO₄] tetrahedra. The [Mo₂O₇]²⁻ in the B layer exhibits a disorder to form a pseudo-[Mo₄O₉] group, in which four Mo and four O sites are half occupied. R(1)³⁺ achieves 8-fold coordination by O²⁻ to form a [R(1)O₈] square antiprism, while R(2)³⁺ achieves 9-fold coordination by O²⁻ and H₂O to form a [R(2)(H₂O)O₈] monocapped square antiprism. The disorder of the [Mo₂O₇]²⁻ group in the B layer induces a large displacement of the O atoms in another [Mo₂O₇]²⁻ group (in the A layer) and in the [R(1)O₈] and [R(2)(H₂O)O₈] polyhedra. A remarkable broadening of the photoluminescence spectrum of Eu₂Mo₆O₂₁·H₂O supported the large displacement of O ligands coordinating Eu(1) and Eu(2).     

U(IV)/LN(III) unexpected mixed site in polymetallic oxalato complexes. Part II. Substitution of U(IV) for Ln(III) in the new oxalates (N2H5)Ln(C2O4)2·nH2O (Ln=Nd, Gd)

Two new hydrazinium lanthanide(III) oxalates, (N₂H₅)[Nd(C₂O₄)₂(H₂O)]·4H₂O (1) and (N₂H₅)[Gd(C₂O₄)₂(H₂O)]·4.5H₂O (2) have been prepared and their crystal structures determined by single-crystal X-ray diffraction. The crystal structures were solved by the direct methods and Fourier difference techniques, and refined by a least-squares method on the basis of F² for all unique reflections. Crystallographic data: 1, triclinic, space group , , b=9.762(4), , α=62.378(5), β=76.681(5), γ=73.858(5), Z=2, R₁=0.0335 for 172 parameters with 3430 reflections with I?2σ(I); 2, triclinic, space group , , b=9.51(3), , α=62.11(4), β=76.15(5), γ=73.73(5), Z=2, R₁=0.0325 for 172 parameters with 1742 reflections with I?2σ(I). The two isotypic structures are built from a three-dimensional (3D) arrangement of lanthanide and oxalate ions. The lanthanide atom is coordinated by eight oxygen atoms from four tetradentate oxalate ions and one aqua oxygen. Alternating lanthanide and oxalate ions form six-membered rings that delimit tunnels running down three directions and occupied by hydrazinium and water molecules. Starting from these lanthanide(III) compounds two isotypic mixed Ln(III)/U(IV) oxalates, (N₂H₅)_0.75[Nd_0.75U_0.25(C₂O₄)₂(H₂O)]·4.5H₂O (3) and (N₂H₅)_0.75[Gd_0.75U_0.25(C₂O₄)₂(H₂O)]·4H₂O (4), are obtained by partial substitution of Ln(III) by U(IV) in the nine-coordinated site, the charge excess being compensated by removal of monovalent ions from the tunnels. Finally, using Na⁺ gel, two mixed Ln(III)/U(IV) sodium oxalates, Na_0.5[Nd_0.5U_0.5(C₂O₄)₂(H₂O)]·3H₂O (5) and Na_0.65[Gd_0.65U_0.35(C₂O₄)₂(H₂O)]·4.5H₂O (6) have been obtained without any change in the 3D framework.     

Preparation, characterization, magnetic susceptibility (Eu, Gd and Sm) and XPS studies of Ln2ZrTiO7 (Ln=La, Eu, Dy and Gd)

Bulk and nanosized pyrochlore materials Ln₂ZrTiO₇ (Ln=La, Eu, Dy, Gd and Sm) have been prepared by the sol-gel method. All the samples were characterized by powder X-ray diffraction, Raman and X-ray photoelectron spectroscopy. Magnetic susceptibility (χ) measurements of Gd₂ZrTiO₇, Sm₂ZrTiO₇ and Eu₂ZrTiO₇ were carried out by vibrating sample magnetometer in the temperature range 2-320 K. The variation of χ⁻¹ (or χ) with temperature of Gd₂ZrTiO₇, Sm₂ZrTiO₇ and Eu₂ZrTiO₇ follows the Curie law, intermediate formula and the Curie-Weiss law, respectively. From the linear portion of χT vs. T⁻¹ plot of Eu₂ZrTiO₇ from 2 to 15 K, the classical nearest neighbor exchange (J^cl) and dipolar interactions (D_nn) are obtained. The XPS of Ln₂ZrTiO₇ (Ln=La, Eu, Dy and Gd) gave characteristic peaks for Ln, Ti, Zr and O. The satellite peaks are observed only for 3d La of La₂ZrTiO₇.     

4,4′-Dipyridyl complexes of rare-earth thiocyanates

4,4-Dipyridyl complexes of rare-earth thiocyanates of the formulaLn(4-dipy)₂(NCS)₃·5H₂O (Ln = La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb, Lu, Y, 4-dipy = 4,4-dipyridyl) have been synthesized. The IR spectra of these compounds and other physical properties are discussed. The thermal decomposition of some compounds (in the order Gd ÷ Lu) has been investigated.

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4,4-Dipyridylkomplexe von Seltenerdmetallthiocyanaten

Zusammenfassung Es wurden 4,4-Dipyridylkomplexe des TypesLn(4-dipy)₂(NCS)₃·5H₂O mitLn = La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb, Lu und Y dargestellt. Die IR-Spektren und andere physikalische Eigenschaften werden diskutiert und die thermische Zersetzung von einigen Verbindungen (in der Reihe Gd ÷ Lu) untersucht.

     

Lanthanide (III) addition of [Mo2O3S(HNTA)2] (Ln=Eu, Dy)

The reactions of LnCl₃·6H₂O (Ln=Eu or Dy) and Na₂[Mo₂O₃S(HNTA)₂]·6H₂O afford Na[Mo₂O₃S(HNTA)₂]₂·Eu(H₂O)₉·3H₂O (1) (NTA=nitrilotriacetate) and Na{(H₂O)₆Dy[Mo₂O₃S(HNTA)₂]₂}·7.5H₂O (2), respectively. The [Mo₂O₃S(HNTA)₂]²⁻ cluster units of 1 are interconnected by Na⁺ into a 3-D open framework with rutile topology templated by . The coordination of [Mo₂O₃S(HNTA)₂]²⁻ to the slightly smaller Dy³⁺ ion of greater ionic potential as a consequence of lanthanide contraction has been observed to form the pentanuclear heterometallic {Dy(H₂O)₆[Mo₂O₃S(HNTA)₂]₂}⁻, which is linked by Na⁺ and hydrogen bonds between the protonated carboxylate groups into a 3-D supramolecular framework. The weak antiferromagnetic interactions between the Dy³⁺ ions of 2 have been observed.     

New insight into the symmetry and the structure of the double perovskites Ba2LnNbO6 (Ln=lanthanides and Y)

Structures of the double perovskites Ba₂LnNbO₆ (Ln=La, Pr, Nd, Sm, Eu, Tb, Dy, Ho, and Y) at room temperature have been re-examined by Rietveld profile analysis of X-ray diffraction data. It was shown that the correct phase sequence across the lanthanides is I2/m (Ln=La, Pr, Nd, and Sm), I4/m (Ln=Eu, Gd, Tb, and Dy), and (Ln=Ho and Y), respectively. All phases can be derived from the ideal cubic perovskite by ordering the Ln(III) and Nb(V) ions and by out-of-phase tilting the LnO₆/NbO₆ octahedra around either the primitive two-fold [110]_p-axis (I2/m) or the four-fold [001]_p-axis (I4/m). The monoclinic P2₁/n structure that contains both out-of-phase and in-phase tilt around the primitive [110]_p- and [001]_p-axis, respectively, has not been observed for this series of compounds.     

Two Ce(SO4)2·4H2O polymorphs: Crystal structure and thermal behavior

Syntheses, crystal structures and thermal behavior of two polymorphic forms of Ce(SO₄)₂·4H₂O are reported. The first modification, α-Ce(SO₄)₂·4H₂O (I), crystallizes in the orthorhombic space group Fddd, with a=5.6587(1), b=12.0469(2), c=26.7201(3) Å and Z=8. The second modification, β-Ce(SO₄)₂·4H₂O (II), crystallizes in the orthorhombic space group Pnma, with a=14.6019(2), b=11.0546(2), c=5.6340(1) Å and Z=4. In both structures, the cerium atoms have eight ligands: four water molecules and four sulfate groups. The mutual position of the ligands differs in (I) and (II), resulting in geometrical isomerism. Both these structures are built up by layers of Ce(H₂O)₄(SO₄)₂ held together by a hydrogen bonding network. The dehydration of Ce(SO₄)₂·4H₂O is a two step (I) and one step (II) process, respectively, forming Ce(SO₄)₂ in both cases. During the decomposition of the anhydrous form, Ce(SO₄)₂, into the final product CeO₂, intermediate xCeO₂·yCe(SO₄)₂ species are formed.