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Title: Rb{sub 2}BaNb{sub 2}Se{sub 11}: A new quaternary niobium polyselenide with infinite anionic chains composed of Nb{sub 2}Se{sub 11} building block

Abstract

The quaternary compound Rb{sub 2}BaNb{sub 2}Se{sub 11} has been synthesized by reacting Nb metal with an in situ formed flux of Rb{sub 2}Se{sub 3}, BaSe and Se at 773 K. Rb{sub 2}BaNb{sub 2}Se{sub 11} crystallizes in the monoclinic space group P2{sub 1}/c with four formula units and lattice parameters a=7.8438(5) A, b=13.6959(6) A, c=17.0677(13) A, {beta}=97.917(9){sup o}. The structure consists of one-dimensional anionic chains formed by interconnection of dimeric [Nb{sub 2}Se{sub 11}] units. The chains are directed along the crystallographic c-axis with Rb{sup +} and Ba{sup 2+} ions being located between the chains. The [Nb{sub 2}Se{sub 11}] units are formed by face sharing of two NbSe{sub 7} bipyramids and are joined by Se{sub 2} {sup 2-} dianions to form infinite {sup 1} {sub {infinity}}[Nb{sub 2}Se{sub 11} {sup 4-}] chains. The compound was characterized with infrared spectroscopy in the FIR region, Raman and UV/Vis diffuse reflectance spectroscopy. - Graphical abstract: The {sup 1} {sub {infinity}}[Nb{sub 2}Se{sub 11}]{sup 4-} chain in the new mixed group1/group2 polyselenide compound Rb{sub 2}BaNb{sub 2}Se{sub 11} is formed by interconnection of [Nb{sub 2}Se{sub 11}] units via Se{sub 2} {sup 2-} dianions. The [Nb{sub 2}Se{sub 11}] building blocks are formed by face sharing of two distorted pentagonal bipyramidalmore » NbSe{sub 7} groups.« less

Authors:
 [1];  [1];  [2]
  1. Institut fuer Anorganische Chemie, Christian-Albrechts-Universitaet zu Kiel, Olshausenstr. 40, D-24108 Kiel (Germany)
  2. Institut fuer Anorganische Chemie, Christian-Albrechts-Universitaet zu Kiel, Olshausenstr. 40, D-24108 Kiel (Germany), E-mail: wbensch@ac.uni-kiel.de
Publication Date:
OSTI Identifier:
21015626
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Solid State Chemistry; Journal Volume: 180; Journal Issue: 1; Other Information: DOI: 10.1016/j.jssc.2006.09.027; PII: S0022-4596(06)00536-6; Copyright (c) 2006 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ABSORPTION SPECTROSCOPY; BARIUM COMPOUNDS; BARIUM IONS; CRYSTALLOGRAPHY; INFRARED SPECTRA; LATTICE PARAMETERS; MONOCLINIC LATTICES; NIOBIUM SELENIDES; RAMAN SPECTROSCOPY; RUBIDIUM COMPOUNDS; RUBIDIUM IONS; SPACE GROUPS; TEMPERATURE RANGE 1000-4000 K

Citation Formats

Wu Yuandong, Naether, Christian, and Bensch, Wolfgang. Rb{sub 2}BaNb{sub 2}Se{sub 11}: A new quaternary niobium polyselenide with infinite anionic chains composed of Nb{sub 2}Se{sub 11} building block. United States: N. p., 2007. Web.
Wu Yuandong, Naether, Christian, & Bensch, Wolfgang. Rb{sub 2}BaNb{sub 2}Se{sub 11}: A new quaternary niobium polyselenide with infinite anionic chains composed of Nb{sub 2}Se{sub 11} building block. United States.
Wu Yuandong, Naether, Christian, and Bensch, Wolfgang. Mon . "Rb{sub 2}BaNb{sub 2}Se{sub 11}: A new quaternary niobium polyselenide with infinite anionic chains composed of Nb{sub 2}Se{sub 11} building block". United States. doi:.
@article{osti_21015626,
title = {Rb{sub 2}BaNb{sub 2}Se{sub 11}: A new quaternary niobium polyselenide with infinite anionic chains composed of Nb{sub 2}Se{sub 11} building block},
author = {Wu Yuandong and Naether, Christian and Bensch, Wolfgang},
abstractNote = {The quaternary compound Rb{sub 2}BaNb{sub 2}Se{sub 11} has been synthesized by reacting Nb metal with an in situ formed flux of Rb{sub 2}Se{sub 3}, BaSe and Se at 773 K. Rb{sub 2}BaNb{sub 2}Se{sub 11} crystallizes in the monoclinic space group P2{sub 1}/c with four formula units and lattice parameters a=7.8438(5) A, b=13.6959(6) A, c=17.0677(13) A, {beta}=97.917(9){sup o}. The structure consists of one-dimensional anionic chains formed by interconnection of dimeric [Nb{sub 2}Se{sub 11}] units. The chains are directed along the crystallographic c-axis with Rb{sup +} and Ba{sup 2+} ions being located between the chains. The [Nb{sub 2}Se{sub 11}] units are formed by face sharing of two NbSe{sub 7} bipyramids and are joined by Se{sub 2} {sup 2-} dianions to form infinite {sup 1} {sub {infinity}}[Nb{sub 2}Se{sub 11} {sup 4-}] chains. The compound was characterized with infrared spectroscopy in the FIR region, Raman and UV/Vis diffuse reflectance spectroscopy. - Graphical abstract: The {sup 1} {sub {infinity}}[Nb{sub 2}Se{sub 11}]{sup 4-} chain in the new mixed group1/group2 polyselenide compound Rb{sub 2}BaNb{sub 2}Se{sub 11} is formed by interconnection of [Nb{sub 2}Se{sub 11}] units via Se{sub 2} {sup 2-} dianions. The [Nb{sub 2}Se{sub 11}] building blocks are formed by face sharing of two distorted pentagonal bipyramidal NbSe{sub 7} groups.},
doi = {},
journal = {Journal of Solid State Chemistry},
number = 1,
volume = 180,
place = {United States},
year = {Mon Jan 15 00:00:00 EST 2007},
month = {Mon Jan 15 00:00:00 EST 2007}
}
  • Rb{sub 12}Nb{sub 6}Se{sub 35} is the first ternary niobium polyselenide composed of infinite anionic chains. These are well separated by rubidium cations. It crystallizes in the orthorhombic space group Pbcn with unit cell dimensions a = 8.5811(1) {angstrom}, b = 13.7152(1) {angstrom}, c = 56.5225(4) {angstrom}, and Z = 4. The least-squares refinement against F{sup 2} with anisotropic displacement parameters for all atoms yields R1 = 5.78 and wR2 = 12.81. The anionic polymeric chains are arranged in layers parallel to the (010) plane, and successive planes are rotated by 35{degree} against each other. Nb{sub 2}Se{sub 11} units composed ofmore » two face-sharing NbSe{sub 7} pentagonal bipyramids are the building blocks of the structure. They are interconnected by Se{sub 2}{sup 2{minus}} and Se{sub 3}{sup 2{minus}} polyanions, giving rise to infinite {sub {infinity}}{sup 1}[Nb{sub 6}Se{sub 35}]{sup 12{minus}} chains. Within the Nb{sub 2}Se{sub 11} units an unusual nearly linear Se{sub 3} fragment is found which must be formulated as Se{sub 3}{sup 4{minus}}.« less
  • The reaction of InCl[sub 3] with Na[sub 2]Se[sub 5] in dimethylformamide (DMF) in the presence of Ph[sub 4]PCl gave (Ph[sub 4]P)[sub 4][In[sub 2](Se[sub 4])[sub 4](Se[sub 5])] (I) in 75% yield. Under the same conditions, InCl[sub 3] reacted with Na[sub 2]Se[sub 5] in the presence of Pr[sub 4]NBr or Et[sub 4]NBr and afforded (Pr[sub 4]N)[sub 4][In[sub 2](Se[sub 4])[sub 4](Se[sub 5])] (II) in 65% yield and (Et[sub 4]N)[sub 4][In[sub 2](Se[sub 4])[sub 4](Se[sub 5])] (III) in 72% yield, respectively. Single-crystal X-ray diffraction studies show that (I), (II), and (III) contain the same anion, [In[sub 2](Se[sub 4])[sub 4](Se[sub 5])][sup 4[minus]]. The anion consists ofmore » In[sup 3+] centers in trigonal bipyramidal coordination; each In atom is chelated by two bidentate Se[sub 4][sup 2[minus]] ligands forming a [In(Se[sub 4])[sub 2]][sup [minus]] unit. Two of these [In(Se[sub 4])[sub 2]][sup [minus]] units are bridged by an Se[sub 5][sup 2[minus]] chain forming a dimer. The hydrothermal reaction of InCl[sub 3] with Na[sub 2]Se[sub 4] in the presence of Pr[sub 4]NBr and water at 110[degrees]C for 3 days in an evacuated sealed Pyrex tube afforded deep red crystals of (Pr[sub 4]N)[sub 2][In[sub 2]Se[sub 2](Se[sub 4])[sub 2]] (IV), in 80% yield. Under the same conditions the reaction with [(Ph[sub 3]P)[sub 2]N]Cl yields [(Ph[sub 3]P)[sub 2]N][sub 2][In[sub 2]Se[sub 2](Se[sub 4])[sub 2]] (V) in 60% yield. Single-crystal X-ray diffraction studies show that (IV) and (V) contain the same binuclear anion [In[sub 2]Se[sub 2](Se[sub 4])[sub 2]][sup 2[minus]]. The reaction of InCl[sub 3] with Na[sub 2]Se[sub 5] in 1:2 mole ratio in acetonitrile in the presence of Et[sub 4]NBr afforded (Et[sub 4]N)[sub 3][In[sub 3]Se[sub 3](Se[sub 4])[sub 3]] (VI). Similar reaction of TlCl with Na[sub 2]Se[sub 5] in 1:2 mole ratio in DMF in the presence of Et[sub 4]NBr gave (Et[sub 4]N)[sub 3][Tl[sub 3]Se[sub 3](Se[sub 4])[sub 3]] (VII). 57 refs., 13 figs., 14 tabs.« less
  • A new caesium uranyl molybdate belonging to the M{sub 6}U{sub 2}Mo{sub 4}O{sub 21} family has been synthesized by solid-state reaction and its structure determined from single-crystal X-ray diffraction data. Contrary to the other alkali uranyl molybdates of this family (A=Na, K, Rb) where molybdenum atoms adopt only tetrahedral coordination and which can be formulated A{sub 6}[(UO{sub 2}){sub 2}O(MoO{sub 4}){sub 4}], the caesium compound Cs{sub 6}U{sub 2}Mo{sub 4}O{sub 21} should be written Cs{sub 6}[(UO{sub 2}){sub 2}(MoO{sub 4}){sub 3}(MoO{sub 5})] with molybdenum atoms in tetrahedral and square pyramidal environments. Cs{sub 6}[(UO{sub 2}){sub 2}(MoO{sub 4}){sub 3}(MoO{sub 5})] crystallizes in the triclinic symmetry withmore » space group P1-bar and a=10.4275(14) A, b=15.075(2) A, c=17.806(2) A, {alpha}=70.72(1){sup o}, {beta}=80.38(1){sup o} and {gamma}=86.39(1){sup o}, V=2604.7(6) A{sup 3}, Z=4, {rho}{sub mes}=5.02(2) g/cm{sup 3} and {rho}{sub cal}=5.08(3) g/cm{sup 3}. A full-matrix least-squares refinement on the basis of F{sup 2} yielded R{sub 1}=0.0464 and wR{sub 2}=0.0950 for 596 parameters with 6964 independent reflections with I{>=}2{sigma}(I) collected on a BRUKER AXS diffractometer with Mo(K{alpha}) radiation and a CCD detector. The crystal structure of Cs compound is characterized by {sub {infinity}}{sup 1}[(UO{sub 2}){sub 2}(MoO{sub 4}){sub 3}(MoO{sub 5})]{sup 6-} parallels chains built from U{sub 2}O{sub 13} dimeric units, MoO{sub 4} tetrahedra and MoO{sub 5} square pyramids, whereas, Na, K and Rb compounds are characterized by {sub {infinity}}{sup 1}[(UO{sub 2}){sub 2}O(MoO{sub 4}){sub 4}]{sup 6-} parallel chains formulated simply of U{sub 2}O{sub 13} units and MoO{sub 4} tetrahedra. Infrared spectroscopy measurements using powdered samples synthesized by solid-state reaction, confirm the structural results. The thermal stability and the electrical conductivity are also studied. The four compounds decompose at low temperature (between 540 and 610 {sup o}C). -- Graphical abstract: The staking of {sub {infinity}}{sup 1}[(UO{sub 2}){sub 2}(MoO{sub 4}){sub 3}(MoO{sub 5})]{sup 6-} infinite uranyl molybdate ribbons in the Cs{sub 6}[(UO{sub 2}){sub 2}(MoO{sub 4}){sub 3}(MoO{sub 5})] structure. Display Omitted Highlights: {yields} Cs{sub 6}U{sub 2}Mo{sub 4}O{sub 2} a new compound with bidimensional crystal structure, characterized by infinite uranyl molybdate chains. {yields} Crystal structure similar to these of the compounds containing Na, K, Rb. {yields} Molybdenum atoms surrounded by five oxygen atoms to form an original and strongly distorted MoO{sub 5} environment. {yields} The chains arrangement illustrates the key role of the alkaline ionic radius, in the crystal structure distortion for Cs compound.« less
  • The synthesis, structural characterization, and reactivity of heavier metal polychalcogenide (i.e. polyselenide and polytelluride) compounds are currently an active area of research after intense studies on metal polysulfides in the last decade. Recently, the authors reported on the chemistry of silver-polyselenide complexes, a system characterized by great structural diversity. Furthermore, their preliminary exploration on the Au/Se{sub x}{sup 2{minus}} system revealed an intriguing and unanticipated redox chemistry. This interesting redox interplay between Au{sup n+} (n = 1,3) and Se{sub x}{sup 2{minus}} incited them to investigate further this system in order to gain more information and insight into the redox behavior ofmore » gold in the presence of Se{sub x}{sup 2{minus}} ligands. In order to influence the aforementioned redox chemistry, they examined the reactivity of AuCN toward less reducible shorter polyselenide Se{sub x}{sup 2{minus}} ligands (i.e. x = 1-4) in the presence of different counterions such as Ph{sub 4}P{sup +}, ((Ph{sub 3}P){sub 2}N){sup +}, Pr{sub 4}N{sup +}, etc. Here they wish to report the newly isolated (Ph{sub 4}P){sub 2}(Au{sub 2}(Se{sub 2})(Se{sub 3})) (I), ((Ph{sub 3}P){sub 2}N){sub 2}(Au{sub 2}(Se{sub 2})(Se{sub 3})) (II), and (Ph{sub 4}P){sub 2}(Au{sub 2}(Se{sub 2})(Se{sub 4})) (III), the first Au(I) polyselenide complexes isolated from solution.« less
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