Syntheses and Crystal Structures of Rare-Earth Oxyapatites Ca2RE8(SiO4)6O2 (RE = Pr,Tb, Ho,Tm)

Journal of Chemical Crystallography - Four different rare-earth oxyapatites of Ca2RE8(SiO4)6O2 (RE?=?Pr, Tb, Ho, Tm) were synthesized using a solution-based method followed by drying,...     

Framework Polymorphism and Modular Crystal Structures of Uranyl Vanadates of Divalent Cations: Synthesis and Characterization of M(UO2)(V2O7) (M = Ca,Sr) and Sr3(UO2)(V2O7)2

Uranyl vanadate compounds with divalent cations, M(UO₂)(V₂O₇) (M = Ca, Sr) and Sr₃(UO₂)(V₂O₇)₂, were synthesized by flux crystal growth, and their crystal structures were solved using single‐crystal X‐ray diffraction data. Ca(UO₂)V₂O₇ and Sr(UO₂)V₂O₇ were synthesized from reactants with molar ratios M:U:V of 1:1:2 and identical heating conditions, and increasing the M:U:V ratio to 3:1:4 resulted in Sr₃(UO₂)(V₂O₇)₂. Crystallographic data for M(UO₂)V₂O₇ compounds are: a = 7.1774(18) Å, b = 6.7753(17) Å, c = 8.308(2) Å; V = 404.01(18) ų; space group Pmn2₁, Z = 2 for Ca; a = 13.4816(11) Å, b = 7.3218(6) Å, c = 8.4886(7) Å; V = 837.91(12) ų; space group Pnma, Z = 4 for Sr. Compound Sr₃(UO₂)(V₂O₇)₂ has a = 6.891(3) Å, b = 7.171(3) Å, c = 14.696(6) Å, α = 85.201(4)?, β = 78.003(4)?, γ = 89.188(4)?; V = 707.9(5) ų; space group P1 , Z = 2. The framework structure of Sr(UO₂)(V₂O₇) is related to that of Pb(UO₂)(V₂O₇) reported previously, while that of Ca(UO₂)(V₂O₇) has a different topology. The topological polymorphism of the [(UO₂)(V₂O₇)]‐type framework may be due to the differing ionic radii of the guest M²⁺ cations. Compound Sr₃(UO₂)(V₂O₇)₂ has a modular structure based on two different types of electroneutral layers: [Sr(UO₂)(V₂O₇)] and [Sr₂(V₂O₇)]. Structural complexities were calculated, and Raman spectra were collected and their peaks were assigned.     

Synthesis of Dysprosium Oxychloride (DyOCl)

Dysprosium oxychloride, DyOCl, was synthesized using a simple hydrolysis method with DyCl₃·6H₂O. X-ray powder diffraction (XRD) data was used to determine the crystal structure. The DyOCl compound is isostructural to the matlockite (PbFCl) crystal structure and crystallizes in the tetragonal P4/nmm (#129) space group. The crystal structure contains the alternating cationic layers of (DyO)_n and anionic layers of nCl^? along the c-axis. The structural data including unit cell, volume, and density of DyOCl were compared to other rare-earth oxychloride data from the Inorganic Crystal Structure Database (ICSD) and our previous study on TbOCl. Fourier-transform infrared spectroscopy was performed on DyOCl and peaks observed at 543 and 744 cm^?1 were attributed to Dy–O and Dy–Cl. Scanning electron microscopy analysis showed irregularly shaped crystals. Hot-stage XRD, thermogravimetry, as well as differential scanning calorimetry coupled to a gas chromatograph and a mass spectrometer (evolved gas analysis) were performed on DyCl₃·6H₂O to understand the phase transformation to DyOCl (and Dy₂O₃) as a function of temperature and time at temperature.

Graphic Abstract

DyOCl compound with the tetragonal P4/nmm space group is composed of the alternating layers of (DyO)_n and nCl^? along the c-axis.