The Crystal Structures of the Hydrated Alkalimetal-/Rare Earth(III) Chlorides ALnCl4· 4H2O (A= NH4, K, Rb, Cs; Ln = La–Sm) and CsLaCl4· 3H2O

The Structure and Synthesis of Plutonium(III) Chlorides from Aqueous Solution

“…The Pu−O distances are also consistent with the Pu−O bond distances reported in the compound [Pu(H 2 O) 9 ][CF 3 SO 3 ] 3 of 2.574 and 2.476 Å 27 and earlier EXAFS studies. , The nearest charge balancing Cs atom is 4.844 Å from the Pu atom. This cis arrangement has been previously demonstrated in La complexes isolated from aqueous solution and U complexes from organic solvents. ,

1 Thermal ellipsoid plot of (a) cis- Cs[PuCl 4 (H 2 O) 4 ] and (b) trans -Cs 5 [PuCl 4 (H 2 O) 4 ]Cl 4 ·2H 2 O at 50% probability.

…”

“…The Pu−O distances for the coordinating water, 2.491(3)−2.567(3) Å, agree with previously reported values for the plutonium(III) aquo ion 27 and are identical with those found in the cis compound. While complexes of similar stoichiometry are known in the lanthanides and U, , this trans arrangement of the Cl atoms is to our best knowledge unreported.…”

Synthesis of Hydrated Ternary Lanthanide-Containing Chlorides Exhibiting X-ray Scintillation and Luminescence

“…In this study, hydrated ternary alkali lanthanide chlorides were crystallized for Eu–Lu as well as for Y. All attempts to obtain similar ternary chloride materials containing the early lanthanides (La–Sm) using the same reaction condition were unsuccessful in yielding new compositions and, instead, resulted in only crystalline products already reported in the literature …”

“…The use of HCl in the reaction mixture aided in the dissolution of reagents, analogous to the role of HF in the mild hydrothermal synthesis of fluorides. − Single crystals of hydrated ternary alkali lanthanide chloride compounds were grown via precipitation from an aqueous solution by slow evaporation of the liquid at room temperature, an approach that had already been found to be extremely effective for crystallizing numerous hydrated ternary fluorides and chlorides exhibiting various structural motifs. − Despite using almost identical reaction conditions for all compositions studied, starting with the lanthanide chloride precursors, the reaction products were found to be quite varied, crystallizing with different compositions and in different structure types. The most likely cause of this variation among the chemically rather similar lanthanides is likely to be found in the lanthanide contraction.…”

“…In this study, hydrated ternary alkali lanthanide chlorides were crystallized for Eu−Lu as well as for Y. All attempts to obtain similar ternary chloride materials containing the early lanthanides (La−Sm) using the same reaction condition were unsuccessful in yielding new compositions and, instead, resulted in only crystalline products already reported in the literature 41. Crystal Structures.The lanthanide chloride series crystallize in six different structure types, Cs 2 EuCl 5 (H 2 O) 10 , C s 7 L n C l 1 0 ( H 2 O ) 8 ( L n = G d o r H o ) , C s 1 0 T b 2 C l 1 7 ( H 2 O ) 1 4 ( H 3 O ) , C s 2 D y C l 5 ( H 2 O ) 6 , Cs 8 Er 3 Cl 17 (H 2 O) 25 , and Cs 5 Ln 2 Cl 11 (H 2 O)…”