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Title: Two new families of lanthanide mixed-ligand complexes, oxalate-carbonate and oxalate-formate: Synthesis and structure of [Ce(H{sub 2}O)]{sub 2}(C{sub 2}O{sub 4}){sub 2}(CO{sub 3}){center_dot}2.5 H{sub 2}O and Ce(C{sub 2}O{sub 4})(HCO{sub 2})

Abstract

Two new families of lanthanide complexes associating the ligand oxalate and carbonate or oxalate and formate have been prepared under autogenous pressure at 200{degrees}C using a pseudo-hydrothermal method. The two families have been extended to some lanthanides (Ln): oxalate-carbonate Ln = Ce, Pr, Nd, and Eu; oxalate-formate Ln = La, Ce, and Sm. The starting suspension contains either oxalate or a mixture of oxalate and oxalic acid. The structures have been solved for the element cerium. In both cases, the structure is built up form cerium atoms sharing all their oxygen atoms with oxalate and carbonate or oxalate and formate ligands thus forming a three-dimensional network. The cerium polyhedra share either faces or edges or corners. The coordination scheme of the oxalate ligands is variable: bischelating, bischelating and monodentate, or bischelating and bismonodentate. The carbonate group acts as a bischelating and bismonodentate ligand while the formate group is chelating and monodentate. The characterization of these two original families by infrared spectra and thermal behavior is presented for some pure phases. A tentative explanation of the synthesis of these two phases will be emphasized.

Authors:
; ;  [1]
  1. CEMES/CNRS, Toulouse (France)
Publication Date:
OSTI Identifier:
508632
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Solid State Chemistry; Journal Volume: 127; Journal Issue: 2; Other Information: PBD: Dec 1996
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 40 CHEMISTRY; OXALATES; CRYSTAL STRUCTURE; CARBONATES; FORMATES; HYDRATES; CERIUM COMPLEXES; CHEMICAL PREPARATION; PRASEODYMIUM COMPLEXES; NEODYMIUM COMPLEXES; EUROPIUM COMPLEXES; LANTHANUM COMPLEXES; SAMARIUM COMPLEXES; ABSORPTION SPECTROSCOPY

Citation Formats

Romero, S., Mosset, A., and Trombe, J.C. Two new families of lanthanide mixed-ligand complexes, oxalate-carbonate and oxalate-formate: Synthesis and structure of [Ce(H{sub 2}O)]{sub 2}(C{sub 2}O{sub 4}){sub 2}(CO{sub 3}){center_dot}2.5 H{sub 2}O and Ce(C{sub 2}O{sub 4})(HCO{sub 2}). United States: N. p., 1996. Web. doi:10.1006/jssc.1996.0382.
Romero, S., Mosset, A., & Trombe, J.C. Two new families of lanthanide mixed-ligand complexes, oxalate-carbonate and oxalate-formate: Synthesis and structure of [Ce(H{sub 2}O)]{sub 2}(C{sub 2}O{sub 4}){sub 2}(CO{sub 3}){center_dot}2.5 H{sub 2}O and Ce(C{sub 2}O{sub 4})(HCO{sub 2}). United States. doi:10.1006/jssc.1996.0382.
Romero, S., Mosset, A., and Trombe, J.C. Sun . "Two new families of lanthanide mixed-ligand complexes, oxalate-carbonate and oxalate-formate: Synthesis and structure of [Ce(H{sub 2}O)]{sub 2}(C{sub 2}O{sub 4}){sub 2}(CO{sub 3}){center_dot}2.5 H{sub 2}O and Ce(C{sub 2}O{sub 4})(HCO{sub 2})". United States. doi:10.1006/jssc.1996.0382.
@article{osti_508632,
title = {Two new families of lanthanide mixed-ligand complexes, oxalate-carbonate and oxalate-formate: Synthesis and structure of [Ce(H{sub 2}O)]{sub 2}(C{sub 2}O{sub 4}){sub 2}(CO{sub 3}){center_dot}2.5 H{sub 2}O and Ce(C{sub 2}O{sub 4})(HCO{sub 2})},
author = {Romero, S. and Mosset, A. and Trombe, J.C.},
abstractNote = {Two new families of lanthanide complexes associating the ligand oxalate and carbonate or oxalate and formate have been prepared under autogenous pressure at 200{degrees}C using a pseudo-hydrothermal method. The two families have been extended to some lanthanides (Ln): oxalate-carbonate Ln = Ce, Pr, Nd, and Eu; oxalate-formate Ln = La, Ce, and Sm. The starting suspension contains either oxalate or a mixture of oxalate and oxalic acid. The structures have been solved for the element cerium. In both cases, the structure is built up form cerium atoms sharing all their oxygen atoms with oxalate and carbonate or oxalate and formate ligands thus forming a three-dimensional network. The cerium polyhedra share either faces or edges or corners. The coordination scheme of the oxalate ligands is variable: bischelating, bischelating and monodentate, or bischelating and bismonodentate. The carbonate group acts as a bischelating and bismonodentate ligand while the formate group is chelating and monodentate. The characterization of these two original families by infrared spectra and thermal behavior is presented for some pure phases. A tentative explanation of the synthesis of these two phases will be emphasized.},
doi = {10.1006/jssc.1996.0382},
journal = {Journal of Solid State Chemistry},
number = 2,
volume = 127,
place = {United States},
year = {Sun Dec 01 00:00:00 EST 1996},
month = {Sun Dec 01 00:00:00 EST 1996}
}
  • New hydrated lanthanide phthalates have been hydrothermally prepared with cerium and neodymium in different reaction media involving water or mixed water-ethanol solvent. The monohydrated Ln{sub 2}(1,2-bdc){sub 3}(H{sub 2}O) (Ln=Ce or Nd) and dihydrated Nd{sub 2}(1,2-bdc){sub 3}(H{sub 2}O){sub 2} forms have been characterized by single-crystal analysis. Their structures consist of infinite inorganic chains of lanthanide-centered polyhedra linked to each other through the phthalate ligands in order to generate mixed organic-inorganic layered structure. The two hydrated structures differ by the number of terminal water species attached to the lanthanide cations, which induce symmetry change from a triclinic (Nd{sub 2}(1,2-bdc){sub 3}(H{sub 2}O){sub 2})more » to an orthorhombic (Nd{sub 2}(1,2-bdc){sub 3}(H{sub 2}O){sub 2}) cell for neodymium whereas the cerium-based phase only exists in the monohydrated form, with two distinct symmetries (orthorhombic or triclinic). Structural comparisons with the other members of the lanthanide phthalate series with identical chemical formula are also discussed. Thermal X-ray diffraction experiment indicates that the transformation from dihydrate form into the monohydrated form does not occur during a heating process. - Graphical abstract: New members of the chain-like structures of neodymium phthalates with different hydration states Nd{sub 2}(1,2-bdc){sub 3}(H{sub 2}O){sub x} (x=1 or 2, 1-2bdc=phthalate group) and comparison with cerium-based analogs.« less
  • Single crystals of two cerium complexes, with mixed-ligands oxalate and glycolate, have been prepared in a closed system, at 200{sup o}C for one month: [Ce{sub 2}(H{sub 2}O){sub 3}](C{sub 2}O{sub 4}){sub 2.5}(H{sub 3}C{sub 2}O{sub 3}) 1 and Ce{sub 2}(C{sub 2}O{sub 4})(H{sub 3}C{sub 2}O{sub 3}){sub 4}2. 1 crystallizes in the orthorhombic system, space group Pbca, with a=13.0090(13)A, b=10.3870(8)A, and a=22.102(3)A while 2 crystallizes in the tetragonal system, space group P4{sub 2}/nbc, with a=11.7030(4)A, c=13.2570(2)A. For both complexes, the three-dimensional framework structure is built up by the linkages of the cerium and all the oxygen atoms of oxalate and glycolate ligands. For 2,more » its structure presents a nice case of two 3D identical sub-lattices, with 2-fold interpenetration. The only link between these two sub-lattices is assumed by strong hydrogen bonds between the hydroxyl function of the glycolate and the oxygen atoms of the oxalate. The schematized framework of 2, including only the cerium atoms, can be compared to that of cooperite (PtS). For 1, the two independent cerium have 9- or 10-fold coordination, forming a distorted monocapped or bicapped square antiprism polyhedron while for 2, the two independent cerium present 8-fold coordination, forming an almost regular dodecahedron. A quite relevant feature of 2 is the complete absence of water. 2 has been extended to other lanthanides (Ln=Ce...Lu, yttrium included) leading to a family, which has been characterized by infra-red and thermal analysis.« less
  • Single crystals of (NH{sub 3}(CH{sub 2}){sub 3}NH{sub 3})(H{sub 3}O){sub 2}(UO{sub 2}){sub 3}(MoO{sub 4}){sub 5} (1), C(NH{sub 2}){sub 3}(UO{sub 2})(OH)(MoO{sub 4}) (2), (C{sub 4}H{sub 12}N{sub 2})(UO{sub 2})(MoO{sub 4}){sub 2} (3) and (C{sub 5}H{sub 14}N{sub 2})(UO{sub 2})(MoO{sub 4}){sub 2}{center_dot}H{sub 2}O (4) have been synthesized hydrothermally by using UO{sub 2}(CH{sub 3}COO){sub 2}{center_dot}2H{sub 2}O, (NH{sub 4}){sub 2}Mo{sub 2}O{sub 7}, HF{sub (aq)}, H{sub 2}O, and the respective organic template. The materials have layered structures with anionic uranium molybdate sheets separated by cationic organic templates. Compound 1 has an unprecedented uranium molybdate topology, whereas 2 is structurally related to johannite, Cu[(UO{sub 2}){sub 2}(SO{sub 4}){sub 2}(OH){sub 2}](H{submore » 2}O){sub 8}, and 3 and f4 have layer topologies similar to zippiete, K{sub 2}[UO{sub 2}(MoO{sub 4}){sub 2}]. Thermogravimetric measurements indicate all that four materials, after template loss, form a crystalline mixture of UO{sub 2}MoO{sub 4} and MoO{sub 3}. Crystal data: (NH{sub 3}(CH{sub 2}){sub 3}(H{sub 3}O){sub 2}(UO{sub 2}){sub 3}(MoO{sub 4}){sub 5}, orthorhombic, space group Pbnm (No. 62), with a = 10.465(1) {angstrom}, b = 16.395(1) {angstrom}, c = 20.241(1) {angstrom}, and Z = 4; C(NH{sub 2}){sub 3}(UO{sub 2})(OH)MoO{sub 4}), monoclinic, space group P2{sub 1}/c (No. 14), with a = 15.411(1) {angstrom}, b = 7.086(1) {angstrom}, c = 18.108(1) {angstrom}, {beta} = 113.125(2){degree}, and Z = 4; (C{sub 4}H{sub 12}N{sub 2})(UO{sub 2})(MoO{sub 4}){sub 2}, triclinic, space group P{bar 1} (No. 2), with a = 7.096(1) {angstrom}, b = 8.388(1) {angstrom}, c = 11.634(1) {angstrom}, {alpha} = 97.008(3){degree}, {beta} = 96.454(2){degree}, {gamma} = 110.456(3){degree}, and Z = 2; (C{sub 5}H{sub 14}N{sub 2})(UO{sub 2})(MoO{sub 4}){sub 2}{center_dot}H{sub 2}O, orthorhombic, space group Pbca (No. 61), with a = 12.697(1) {angstrom}, b = 13.247(1) {angstrom}, c = 17.793(1) {angstrom}, and Z = 8.« less
  • Fe(II)C{sub 2}H{sub 5}PO{sub 3}{center_dot}H{sub 2}O has been prepared via prolonged reaction between iron oxychloride and ethylphosphonic acid in acetone, in a sealed tube. The lamellar structure is very similar to that of previously reported divalent metal phosphonates M(II)(RPO{sub 3}){center_dot}H{sub 2}O (M = Mg, Mn, Ni, Zn). The compound shows sign of 2D antiferromagnetic correlations above the Neel temperature T{sub N} = 24K and a weak ferromagnetic behavior is observed below T{sub N}. The authors also report on the preparation methods and the crystal structures of two new anhydrous copper phosphonates {alpha}-Cu(II)(C{sub 2}H{sub 5}PO{sub 3}), and {beta}-Cu(II)(CH{sub 3}PO{sub 3}) which exhibitsmore » an original tubular three-dimensional structure. The reactivity of bulky phosphonic acids is also described, with the case of Co(II)(t-C{sub 4}H{sub 9}PO{sub 3}){center_dot}H{sub 2}O.« less
  • Although thiolate ligands have been used to separate heavy metal ions from dilute solution, typical uranophilic ligands not unexpectedly contain oxygen and/or nitrogen donors with few examples of thiolate types. In fact, structurally characterized compounds of the uranyl group with sulfur donor ligands in general are largely restricted to 1,1-dithio acid types and thioether and thione groups, with a single reported example of a thiolate type in the mercaptopyridine N-oxide complex [UO{sub 2}(ONC{sub 5}H{sub 4}S){sub 2}(dmso)]. In the course of there investigations of the general coordination chemistry of thiopyrimidine and thiopyridine ligand types, the authors have prepared solutions of uranylmore » thiolate complexes which upon exposure to atmospheric oxygen yield crystalline materials that have been identified as the unusual binuclear thiolate-ligated peroxo complexes [HNEt{sub 3}]{sub 2}-[(UO{sub 2}){sub 2}(O{sub 2})(SC{sub 4}N{sub 2}H{sub 3}){sub 4}] (1) and [HNEt{sub 3}][H(UO{sub 2}){sub 2}(O{sub 2})(SC{sub 4}N{sub 2}H{sub 2}-Me){sub 4}]{center_dot}Me{sub 2}CO{center_dot}0.5Et{sub 3}N (2). While numerous peroxyuranates have been prepared, only oxygen hetero ligands have been previously employed, and despite the enhanced complex stability endowed by such coligands, structural characterization of peroxyuranates has remained elusive.« less