U(IV)/LN(III) unexpected mixed site in polymetallic oxalato complexes. Part II. Substitution of U(IV) for Ln(III) in the new oxalates (N{sub 2}H{sub 5})Ln(C{sub 2}O{sub 4}){sub 2}.nH{sub 2}O (Ln=Nd, Gd)
- Laboratoire de Cristallochimie et Physicochimie du Solide, UMR CNRS 8012, ENSCL-USTL, B.P. 90108, 59652 Villeneuve d'Ascq Cedex (France)
- Laboratoire de Chimie des Actinides, CEA VALRHO/DRCP/SCPS, Ba-hat t 399 BP 17171, 30208 Bagnols sur Ceze Cedex (France)
Two new hydrazinium lanthanide(III) oxalates (N{sub 2}H{sub 5})[Nd(C{sub 2}O{sub 4}){sub 2}(H{sub 2}O)].4H{sub 2}O (1) and (N{sub 2}H{sub 5})[Gd(C{sub 2}O{sub 4}){sub 2}(H{sub 2}O)].4.5H{sub 2}O (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 F{sup 2} for all unique reflections. Crystallographic data: 1, triclinic, space group P1-bar , a=8.507(3)A, b=9.762(4), c=10.249(4)A, {alpha}=62.378(5), {beta}=76.681(5), {gamma}=73.858(5), Z=2, R{sub 1}=0.0335 for 172 parameters with 3430 reflections with I>=2{sigma}(I); 2, triclinic, space group P1-bar , a=8.52(3)A, b=9.51(3), c=10.14(3)A, {alpha}=62.11(4), {beta}=76.15(5), {gamma}=73.73(5), Z=2, R{sub 1}=0.0325 for 172 parameters with 1742 reflections with I>=2{sigma}(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 (N{sub 2}H{sub 5}){sub 0.75}[Nd{sub 0.75}U{sub 0.25}(C{sub 2}O{sub 4}){sub 2}(H{sub 2}O)].4.5H{sub 2}O (3) and (N{sub 2}H{sub 5}){sub 0.75}[Gd{sub 0.75}U{sub 0.25}(C{sub 2}O{sub 4}){sub 2}(H{sub 2}O)].4H{sub 2}O (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{sup +} gel, two mixed Ln(III)/U(IV) sodium oxalates, Na{sub 0.5}[Nd{sub 0.5}U{sub 0.5}(C{sub 2}O{sub 4}){sub 2}(H{sub 2}O)].3H{sub 2}O (5) and Na{sub 0.65}[Gd{sub 0.65}U{sub 0.35}(C{sub 2}O{sub 4}){sub 2}(H{sub 2}O)].4.5H{sub 2}O (6) have been obtained without any change in the 3D framework.
- OSTI ID:
- 20721726
- Journal Information:
- Journal of Solid State Chemistry, Vol. 178, Issue 10; Other Information: DOI: 10.1016/j.jssc.2005.06.032; PII: S0022-4596(05)00296-3; Copyright (c) 2005 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved; Country of input: International Atomic Energy Agency (IAEA); ISSN 0022-4596
- Country of Publication:
- United States
- Language:
- English
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