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Title: Synthesis, Crystal Structure, Polymorphism, and Magnetism of Eu(CN3H4)2 and First Evidence of EuC(NH)3

Authors:
; ; ;
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
Sponsoring Org.:
FOREIGN
OSTI Identifier:
1343995
Resource Type:
Journal Article
Resource Relation:
Journal Name: Inorganics; Journal Volume: 5; Journal Issue: 1
Country of Publication:
United States
Language:
ENGLISH

Citation Formats

Görne, Arno, George, Janine, van Leusen, Jan, and Dronskowski, Richard. Synthesis, Crystal Structure, Polymorphism, and Magnetism of Eu(CN3H4)2 and First Evidence of EuC(NH)3. United States: N. p., 2017. Web. doi:10.3390/inorganics5010010.
Görne, Arno, George, Janine, van Leusen, Jan, & Dronskowski, Richard. Synthesis, Crystal Structure, Polymorphism, and Magnetism of Eu(CN3H4)2 and First Evidence of EuC(NH)3. United States. doi:10.3390/inorganics5010010.
Görne, Arno, George, Janine, van Leusen, Jan, and Dronskowski, Richard. Tue . "Synthesis, Crystal Structure, Polymorphism, and Magnetism of Eu(CN3H4)2 and First Evidence of EuC(NH)3". United States. doi:10.3390/inorganics5010010.
@article{osti_1343995,
title = {Synthesis, Crystal Structure, Polymorphism, and Magnetism of Eu(CN3H4)2 and First Evidence of EuC(NH)3},
author = {Görne, Arno and George, Janine and van Leusen, Jan and Dronskowski, Richard},
abstractNote = {},
doi = {10.3390/inorganics5010010},
journal = {Inorganics},
number = 1,
volume = 5,
place = {United States},
year = {Tue Feb 07 00:00:00 EST 2017},
month = {Tue Feb 07 00:00:00 EST 2017}
}
  • Co[(CH{sub 3}PO{sub 3})(H{sub 2}O)] (1) and Co[(C{sub 2}H{sub 5}PO{sub 3})(H{sub 2}O)] (2) were prepared by the hydrothermal method and isolated as blue-violet platelet crystals. They were characterized by X-ray diffraction, FT-IR, TGA-DSC techniques and their magnetic properties studied by a dc-SQUID magnetometer. Compound (1) shows an hybrid layered structure, made of alternating inorganic and organic layers along the a-direction of the unit cell. The inorganic layers contain Co(II) ions six-coordinated by five phosphonate oxygen atoms and one from the water molecule. These layers are separated by bi-layers of methyl groups and van der Waals contacts are established between them. Inmore » compound (2), the layered hybrid structure is rather similar to that described for compound (1), but the alternation of the inorganic and organic layers is along the b-direction of the unit cell. The magnetic behavior of (1) and (2) as function of temperature and magnetic field was studied. The compounds obey the Curie-Weiss law at temperatures above 100K, the Curie C, and Weiss {theta} constants for the methyl derivative being C=3.36cm{sup 3}Kmol{sup -1} and {theta}=-53K and for the ethyl derivative C=3.62cm{sup 3}Kmol{sup -1} and {theta}=-75K, respectively. The observed magnetic moments for Co atom at room temperature (i.e. {mu}{sub eff}=5.18 and 5.38 BM, respectively) are higher than those expected for a spin-only value for high spin Co(II) (S=3/2), revealing a substantial orbital contribution to the magnetic moment. The negative values of {theta} are an indication of the presence of antiferromagnetic exchange couplings between the near-neighbors Co(II) ions, within the layers. [Co(C{sub n}H{sub 2n+1}PO{sub 3})(H{sub 2}O)] (n=1,2) are 2D Ising antiferromagnets at low temperatures.« less
  • K{sub 2}Li(NH{sub 2}){sub 3} (1) was the only crystalline product obtained from the reaction of potassium with dilithium decahydro-closo-decaborate Li{sub 2}B{sub 10}H{sub 10} in liquid ammonia at -38{sup o}C. The compound crystallizes in the space group P4{sub 2}/m with Z=4, a=6.8720(5)A, c=11.706(1)A and V=552.81(7)A{sup 3}. The investigated crystal-chemically isotypic sodium compound K{sub 2}Na(NH{sub 2}){sub 3} (2) was merohedrally twinned and crystallized from a reaction mixture containing potassium and disodium decahydro-closo-decaborate Na{sub 2}B{sub 10}H{sub 10} in liquid ammonia with a=7.0044(5)A, c=12.362(1)A and V=606.48(9)A{sup 3}. The compounds contain pairs of edge sharing tetraamidolithium or tetraamidosodium tetrahedra which are interconnected by potassium ionsmore » forming three-dimensional infinite networks.« less
  • Four new Li uranyl phosphates and arsenates have been prepared by high-temperature solid-state reactions: {alpha}-Li[(UO{sub 2})(PO{sub 4})] (1), {alpha}-Li[(UO{sub 2})(AsO{sub 4})] (2), {beta}-Li[(UO{sub 2})(AsO{sub 4})] (3) and Li{sub 2}[(UO{sub 2}){sub 3}(P{sub 2}O{sub 7}){sub 2}] (4). The structures of the compounds have been solved by direct methods: 1-triclinic, P1-bar, a=5.0271(1) A, b=9.8799(2) A, c=10.8920(2) A, {alpha}=108.282(9){sup o}, {beta}=102.993(8){sup o}, {gamma}=104.13(1){sup o}, V=470.69(2) A{sup 3}, Z=4, R{sub 1}=0.0415 for 2786 unique reflections with |F{sub 0}|{>=}4{sigma}{sub F}; 2-triclinic, P1-bar, a=5.129(2) A, b=10.105(3) A, c=11.080(3) A, {alpha}=107.70(2){sup o}, {beta}=102.53(3){sup o}, {gamma}=104.74(3){sup o}, V=501.4(3) A{sup 3}, Z=4, R{sub 1}=0.055 for 1431 unique reflections with |F{submore » 0}|{>=}4{sigma}{sub F}; 3-triclinic, P1-bar, a=5.051(1) A, b=5.303(1) A, c=10.101(1) A, {alpha}=90.31(1){sup o}, {beta}=97.49(1){sup o}, {gamma}=105.08(1){sup o}, V=258.80(8) A{sup 3}, Z=2, R{sub 1}=0.0339 for 2055 unique reflections with |F{sub 0}|{>=}4{sigma}{sub F}; 4-triclinic, P1-bar, a=5.312(1) A, b=6.696(1) A, c=12.542(1) A, {alpha}=94.532(9){sup o}, {beta}=99.059(8){sup o}, {gamma}=110.189(7){sup o}, V=409.17(10) A{sup 3}, Z=2, R{sub 1}=0.0565 for 1355 unique reflections with |F{sub 0}|{>=}4{sigma}{sub F}. The structures of all four compounds are based upon 3-D frameworks of U and T polyhedra (T=P, As). Phases 1 and 2 are isostructural and consist of U{sub 2}O{sub 12} dimers and UO{sub 6} square bipyramids linked by single TO{sub 4} tetrahedra. The structure of 3 consists of 3-D framework of corner-sharing UO{sub 6} bipyramids and AsO{sub 4} tetrahedra. In the structure of 4, the framework is composed of U{sub 2}O{sub 12} dimers, UO{sub 6} bipyramids and P{sub 2}O{sub 7} dimers. In all the compounds, Li{sup +} cations reside in framework cavities. The topologies of the 3-D frameworks can be described as derivatives of the PtS (cooperite) network. - Graphical abstract: Polyhedral and topological presentation of Li{sub 2}[(UO{sub 2}){sub 3}(P{sub 2}O{sub 7}){sub 2}] crystal structure.« less
  • Using tris(2-ethylamino)amine (tren) as a template, three new fluorides are obtained by solvothermal synthesis: [(C{sub 2}H{sub 4}NH{sub 3}){sub 3}NH].[Zr{sub 3}F{sub 16}(H{sub 2}O)] (I), [(C{sub 2}H{sub 4}NH{sub 3}){sub 3}N]{sub 2}.[ZrF{sub 6}].[Zr{sub 2}F{sub 12}] (II) and [(C{sub 2}H{sub 4}NH{sub 3}){sub 3}N].[TaF{sub 7}].F (III). The structure determinations are performed by single crystal technique. The structure of I consists of infinite spiral-like [Zr{sub 3}F{sub 16}(H{sub 2}O)]{sup 4-} chains connected by tetraprotonated [trenH{sub 4}]{sup 4+} cations which possess a plane configuration. In II, isolated [ZrF{sub 6}] octahedra or [Zr{sub 2}F{sub 12}] dimers are linked to organic cations by a tridimensional hydrogen bond network. In III,more » [TaF{sub 7}]{sup 2-} monocapped trigonal prisms and 'isolated' fluoride ions are connected by hydrogen bonds to template moieties. In II and III, every organic moiety is triprotonated [trenH{sub 3}]{sup 3+} with a 'spider' configuration. In the tantalum phase, the hydrogen bond network leads to the formation of a layered structure.« less
  • The complex (LRe(NO)(CO)(NCO))(BF/sub 4/) (1) has been synthesized from (LRe(NO)(CO)/sub 2/)(BF/sub 4/)/sub 2/ (L = 1,4,7-triazacyclononane, C/sub 6/H/sub 15/N/sub 3/) in methanol with a variety of nucleophiles such as N/sub 2/H/sub 4/ x H/sub 2/O, H/sub 2/NNH(CH/sub 3/), H/sub 2/NN(CH/sub 3/)/sub 2/, H/sub 2/NOH, and N/sub 3//sup -/. The kinetics and mechanisms of the formation of 1 have been investigated. A general mechanisms for these reactions is proposed: nucleophilic attack at a coordinated carbonyl produces carbazoyl intermediates when hydrazine or its N-methylated derivatives are reactants. In the rate-determining step, NH/sub 3/, NH/sub 2/(CH/sub 3/), or NH(CH/sub 3/)/sub 2/ is thenmore » cleaved off and fast rearrangement to the N-coordinated isocyanate occurs. 1 undergoes a series of reactions at the coordinated isocyanate ligand; e.g. concentrated HBr reacts in CH/sub 3/OH with 1 to produce (LRe(NO)(CO)(NH/sub 3/))Br/sub 2/ (3), the crystal structure of which has been determined by X-ray crystallography. The kinetics and mechanisms of the reaction of 1 with H/sup +/ to produce 3 and CO/sub 2/ have been investigated. 3 is electrochemically or chemically oxidized to paramagnetic (LRe(NO)(CO)(NH/sub 3/))Br/sub 3/. The reaction of 1 with concentrated formic acid, trifluoromethanesulfonic acid and iodide anion were investigated, and the products of the reactions are reported. Spectroscopic properties (/sup 1/H and /sup 13/C NMR, vis, ir) are reported for all compounds. 38 references, 5 figures, 6 tables.« less