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Title: Yb{sub 5}Ni{sub 4}Sn{sub 10} and Yb{sub 7}Ni{sub 4}Sn{sub 13}: New polar intermetallics with 3D framework structures

Abstract

The title compounds have been obtained by solid state reactions of the corresponding pure elements at high temperature, and structurally characterized by single-crystal X-ray diffraction studies. Yb{sub 5}Ni{sub 4}Sn{sub 10} adopts the Sc{sub 5}Co{sub 4}Si{sub 10} structure type and crystallizes in the tetragonal space group P4/mbm (No. 127) with cell parameters of a=13.785(4) A, c=4.492 (2) A, V=853.7(5) A{sup 3}, and Z=2. Yb{sub 7}Ni{sub 4}Sn{sub 13} is isostructural with Yb{sub 7}Co{sub 4}InGe{sub 12} and crystallizes in the tetragonal space group P4/m (No. 83) with cell parameters of a=11.1429(6) A, c=4.5318(4) A, V=562.69(7) A{sup 3}, and Z=1. Both structures feature three-dimensional (3D) frameworks based on three different types of one-dimensional (1D) channels, which are occupied by the Yb atoms. Electronic structure calculations based on density functional theory (DFT) indicate that both compounds are metallic. These results are in agreement with those from temperature-dependent resistivity and magnetic susceptibility measurements. - Graphical abstract: Two new ytterbium nickel stannides, namely, Yb{sub 5}Ni{sub 4}Sn{sub 10} and Yb{sub 7}Ni{sub 4}Sn{sub 13}, have been synthesized and structurally characterized by single-crystal X-ray diffraction studies. Both their structures feature three-dimensional (3D) frameworks based on three different types of one-dimensional (1D) channels, which are situated by all the Yb atoms.more » Electronic structure calculations based on density functional theory (DFT) indicate that both compounds are metallic, which are in accordance with the results from temperature-dependent resistivity and magnetic susceptibility measurements.« less

Authors:
; ;  [1];  [2]; ;  [1];  [1]
  1. State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002 (China)
  2. (China)
Publication Date:
OSTI Identifier:
21372573
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Solid State Chemistry; Journal Volume: 183; Journal Issue: 4; Other Information: DOI: 10.1016/j.jssc.2010.02.004; PII: S0022-4596(10)00049-6; Copyright (c) 2010 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved.
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; DENSITY FUNCTIONAL METHOD; ELECTRONIC STRUCTURE; INTERMETALLIC COMPOUNDS; MAGNETIC SUSCEPTIBILITY; MONOCRYSTALS; NICKEL COMPOUNDS; SPACE GROUPS; TEMPERATURE DEPENDENCE; TETRAGONAL LATTICES; TIN COMPOUNDS; X-RAY DIFFRACTION; YTTERBIUM COMPOUNDS; ALLOYS; CALCULATION METHODS; COHERENT SCATTERING; CRYSTAL LATTICES; CRYSTAL STRUCTURE; CRYSTALS; DIFFRACTION; MAGNETIC PROPERTIES; PHYSICAL PROPERTIES; RARE EARTH COMPOUNDS; SCATTERING; SYMMETRY GROUPS; TRANSITION ELEMENT COMPOUNDS; VARIATIONAL METHODS

Citation Formats

Lei Xiaowu, Sun Zhongming, Li Longhua, Graduate School of the Chinese Academy of Sciences, Beijing 100039, Zhong Guohua, Hu Chunli, and Mao Jianggao, E-mail: mjg@fjirsm.ac.c. Yb{sub 5}Ni{sub 4}Sn{sub 10} and Yb{sub 7}Ni{sub 4}Sn{sub 13}: New polar intermetallics with 3D framework structures. United States: N. p., 2010. Web.
Lei Xiaowu, Sun Zhongming, Li Longhua, Graduate School of the Chinese Academy of Sciences, Beijing 100039, Zhong Guohua, Hu Chunli, & Mao Jianggao, E-mail: mjg@fjirsm.ac.c. Yb{sub 5}Ni{sub 4}Sn{sub 10} and Yb{sub 7}Ni{sub 4}Sn{sub 13}: New polar intermetallics with 3D framework structures. United States.
Lei Xiaowu, Sun Zhongming, Li Longhua, Graduate School of the Chinese Academy of Sciences, Beijing 100039, Zhong Guohua, Hu Chunli, and Mao Jianggao, E-mail: mjg@fjirsm.ac.c. Thu . "Yb{sub 5}Ni{sub 4}Sn{sub 10} and Yb{sub 7}Ni{sub 4}Sn{sub 13}: New polar intermetallics with 3D framework structures". United States. doi:.
@article{osti_21372573,
title = {Yb{sub 5}Ni{sub 4}Sn{sub 10} and Yb{sub 7}Ni{sub 4}Sn{sub 13}: New polar intermetallics with 3D framework structures},
author = {Lei Xiaowu and Sun Zhongming and Li Longhua and Graduate School of the Chinese Academy of Sciences, Beijing 100039 and Zhong Guohua and Hu Chunli and Mao Jianggao, E-mail: mjg@fjirsm.ac.c},
abstractNote = {The title compounds have been obtained by solid state reactions of the corresponding pure elements at high temperature, and structurally characterized by single-crystal X-ray diffraction studies. Yb{sub 5}Ni{sub 4}Sn{sub 10} adopts the Sc{sub 5}Co{sub 4}Si{sub 10} structure type and crystallizes in the tetragonal space group P4/mbm (No. 127) with cell parameters of a=13.785(4) A, c=4.492 (2) A, V=853.7(5) A{sup 3}, and Z=2. Yb{sub 7}Ni{sub 4}Sn{sub 13} is isostructural with Yb{sub 7}Co{sub 4}InGe{sub 12} and crystallizes in the tetragonal space group P4/m (No. 83) with cell parameters of a=11.1429(6) A, c=4.5318(4) A, V=562.69(7) A{sup 3}, and Z=1. Both structures feature three-dimensional (3D) frameworks based on three different types of one-dimensional (1D) channels, which are occupied by the Yb atoms. Electronic structure calculations based on density functional theory (DFT) indicate that both compounds are metallic. These results are in agreement with those from temperature-dependent resistivity and magnetic susceptibility measurements. - Graphical abstract: Two new ytterbium nickel stannides, namely, Yb{sub 5}Ni{sub 4}Sn{sub 10} and Yb{sub 7}Ni{sub 4}Sn{sub 13}, have been synthesized and structurally characterized by single-crystal X-ray diffraction studies. Both their structures feature three-dimensional (3D) frameworks based on three different types of one-dimensional (1D) channels, which are situated by all the Yb atoms. Electronic structure calculations based on density functional theory (DFT) indicate that both compounds are metallic, which are in accordance with the results from temperature-dependent resistivity and magnetic susceptibility measurements.},
doi = {},
journal = {Journal of Solid State Chemistry},
number = 4,
volume = 183,
place = {United States},
year = {Thu Apr 15 00:00:00 EDT 2010},
month = {Thu Apr 15 00:00:00 EDT 2010}
}
  • Two new ternary ytterbium transition metal stannides, namely, Yb{sub 3}CoSn{sub 6} and Yb{sub 4}Mn{sub 2}Sn{sub 5}, have been obtained by solid-state reactions of the corresponding pure elements in welded tantalum tubes at high temperature. Their crystal structures have been established by single-crystal X-ray diffraction studies. Yb{sub 3}CoSn{sub 6} crystallizes in the orthorhombic space group Cmcm (no. 63) with cell parameters of a=4.662(2), b=15.964(6), c=13.140(5) A, V=978.0(6) A{sup 3}, and Z=4. Its structure features a three-dimensional (3D) open-framework composed of unusual [CoSn{sub 3}] layers interconnected by zigzag Sn chains, forming large tunnels along the c-axis which are occupied by the ytterbiummore » cations. Yb{sub 4}Mn{sub 2}Sn{sub 5} is monoclinic space group C2/m (no. 12) with cell parameters of a=16.937(2), b=4.5949(3), c=7.6489(7) A, {beta}=106.176(4){sup o}, V=571.70(8) A{sup 3}, and Z=2. It belongs to the Mg{sub 5}Si{sub 6} structure type and its anionic substructure is composed of parallel [Mn{sub 2}Sn{sub 2}] ladders interconnected by unusual zigzag [Sn{sub 3}] chains, forming large tunnels along the c-axis, which are filled by the ytterbium cations. Band structure calculations based on density function theory methods were also made for both compounds. - Graphic abstract: Yb{sub 3}CoSn{sub 6} and Yb{sub 4}Mn{sub 2}Sn{sub 5} have been prepared and structurally characterized. Yb{sub 3}CoSn{sub 6} features a 3D open-framework composed of novel [CoSn{sub 3}] layers interconnected by the zigzag Sn chains whereas the anionic substructure of Yb{sub 4}Mn{sub 2}Sn{sub 5} is composed of parallel [Mn{sub 2}Sn{sub 2}] ladders interconnected by the unusual one-dimensional (1D) chains formed by linear [Sn{sub 3}] trimers.« less
  • Single crystals of the new compounds Li{sub 6}[(UO{sub 2}){sub 12}(PO{sub 4}){sub 8}(P{sub 4}O{sub 13})] (1), Li{sub 5}[(UO{sub 2}){sub 13}(AsO{sub 4}){sub 9}(As{sub 2}O{sub 7})] (2), Li[(UO{sub 2}){sub 4}(AsO{sub 4}){sub 3}] (3) and Li{sub 3}[(UO{sub 2}){sub 7}(AsO{sub 4}){sub 5}O)] (4) have been prepared using high-temperature solid state reactions. The crystal structures have been solved by direct methods: 1-monoclinic, C2/m, a=26.963(3) A, b=7.063(1) A, c=19.639(1) A, beta=126.890(4){sup o}, V=2991.2(6) A{sup 3}, Z=2, R{sub 1}=0.0357 for 3248 unique reflections with |F{sub 0}|>=4sigma{sub F}; 2-triclinic, P1-bar, a=7.1410(8) A, b=13.959(1) A, c=31.925(1) A, alpha=82.850(2){sup o}, beta=88.691(2){sup o}, gamma=79.774(3){sup o}, V=3107.4(4) A{sup 3}, Z=2, R{sub 1}=0.0722 formore » 9161 unique reflections with |F{sub 0}|>=4sigma{sub F}; 3-tetragonal, I4{sub 1}/amd, a=7.160(3) A, c=33.775(9) A, V=1732(1) A{sup 3}, Z=4, R{sub 1}=0.0356 for 318 unique reflections with |F{sub 0}|>=4sigma{sub F}; 4-tetragonal, P4-bar, a=7.2160(5) A, c=14.6540(7) A, V=763.04(8) A{sup 3}, Z=1, R{sub 1}=0.0423 for 1600 unique reflections with |F{sub 0}|>=4sigma{sub F}. Structures of all the phases under consideration are based on complex 3D frameworks consisting of different types of uranium polyhedra (UO{sub 6} and UO{sub 7}) and different types of tetrahedral TO{sub 4} anions (T=P or As): PO{sub 4} and P{sub 4}O{sub 13} in 1, AsO{sub 4} and As{sub 2}O{sub 7} in 2, and single AsO{sub 4} tetrahedra in 3 and 4. In the structures of 1 and 2, UO{sub 7} pentagonal bipyramids share edges to form (UO{sub 5}){sub i}nfinity chains extended along the b axis in 1 and along the a axis in 2. The chains are linked via single TO{sub 4} tetrahedra into tubular units with external diameters of 11 A in 1 and 11.5 A in 2, and internal diameters of 4.1 A in 1 and 4.5 A in 2. The channels accommodate Li{sup +} cations. The tubular units are linked into 3D frameworks by intertubular complexes. Structures of 3 and 4 are based on 3D frameworks composed on layers united by (UO{sub 5}){sub i}nfinity infinite chains. Cation-cation interactions are observed in 2, 3, and 4. In 2, the structure contains a trimeric unit with composition [O=U(1)=O]-U(13)-[O=U(2)=O]. In the structures of 3 and 4, T-shaped dimers are observed. In all the structures, Li{sup +} cations are located in different types of cages and channels and compensate negative charges of anionic 3D frameworks. - Graphical abstract: The crystal structures of Li{sub 5}[(UO{sub 2}){sub 13}(AsO{sub 4}){sub 9}(As{sub 2}O{sub 7})] separated into tubular units and intertubular complexes.« less
  • The syntheses of the title compounds are described in detail. Structural characterizations from refinements of single crystal X-ray diffraction data for Yb{sub 5}Bi{sub 3}H{sub x} and Sm{sub 5}Bi{sub 3}H{sub a}pprox{sub 1} and of powder neutron diffraction data for Ca{sub 5}Bi{sub 3}D{sub 0.93(3)} are reported. These confirm that all three crystallize with the heavy atom structure type of beta-Yb{sub 5}Sb{sub 3}, and the third gives the first proof that the deuterium lies in the center of nominal calcium tetrahedra, isostructural with the Ca{sub 5}Sb{sub 3}F-type structure. These Ca and Yb phases are particularly stable with respect to dissociation to Mn{sub 5}Si{submore » 3}-type product plus H{sub 2}. Some contradictions in the literature regarding Yb{sub 5}Sb{sub 3} and Yb{sub 5}Sb{sub 3}H{sub x} phases are considered in terms of adventitious hydrogen impurities that are generated during reactions in fused silica containers at elevated temperatures. - Graphical abstract: The structure of Ca{sub 5}Bi{sub 3}H{sub 0.93} occurs in the novel Ca{sub 5}Sb{sub 3}F structure type with D centered in the shaded calcium tetrahedra.« less
  • The crystal structures of two new compounds were determined from single-crystal X-ray diffraction measurements: Ni{sub 3+x}Sn{sub 4}Zn, (x~1.35, a=7.110(2) Å, b=4.123(1) Å, c=10.346(3) Å, β=90.23(2)°, space group I2/m, Z=2. R1=0.025, wR2=0.059 for 748 unique reflections, 35 variable parameters) and Ni{sub 6+x}Sn{sub 8}Zn, x~1.35 (a=12.379(3) Å, b=4.095(1) Å, c=12.155(3) Å, β=116.25(3)°, space group C2/m, Z=2. R1=0.026, wR2=0.052 for 1346 unique reflections, 60 variable parameters). In addition, a structural refinement was performed for Ni{sub 3+x}Sn{sub 4}, x~0.13 (a=12.264(3) Å, b=4.066(1) Å, c=5.223(2) Å, β=104.85(3)°, space group C2/m, Z=2. R1=0.019, wR2=0.046 for 617 unique reflections, 29 variable parameters). The three compounds show pronouncedmore » similarities among each other as well as to the crystal structures of surrounding binary Ni–Sn and ternary Ni–Sn–Zn compounds. In particular, the two new compounds form a homologous series with Ni{sub 3+x}Sn{sub 4}, x~0.13. They contain “Ni{sub 4}Sn{sub 4}” and “Ni{sub 2}Sn{sub 4}” building blocks which by different interconnection build up the distinct structures. Topological relations with NiSn and Ni{sub 5−δ}Sn{sub 4}Zn, δ~0.25 are evident. - Graphical abstract: Projection of the structure of Ni{sub 6+x}ZnSn{sub 8}, x~1.35 and constituent building blocks. Display Omitted - Highlights: • The crystal structures of Ni{sub 6+x}Sn{sub 8}Zn and Ni{sub 3+x}Sn{sub 4}Zn were determined using single crystal XRD. • Topological relations to Ni–Sn and Ni–Sn–Zn compounds were established and discussed. • Common structural units were identified and their interconnection patterns described.« less
  • Hydrothermal reactions of molybdenum-oxide precursors with polyalcohols in the presence of base yielded two series of mixed-valence oxomolybdenum clusters, the hexadecanuclear species [XH{sub 12}(Mo{sup VI}O{sub 3}){sub 4}Mo{sup V}{sub 12}O{sub 40}]{sup m{minus}}(X=Na{sup +}, m=7; X=2H{sup +}, m=6) and the superclusters [XH{sub n}Mo{sup VI}{sub 6}Mo{sup V}{sub 36}O{sub 109}(OCH{sub 2}){sub 3}CR{sub 7}]{sup m{minus}} (X=Na-(H{sub 2}O){sub 3}{sup +}, m=9, n=13; X=Na(H{sub 2}O){sub 3}{sup +}, m=7, n=15; X=MoO{sub 3}, m=9, n=14; X=MoO{sub 3}, m=10, n=13). In a representative synthesis for the hexadencanuclear class of materials, the hydrothermal reaction of a mixture of Na{sub 2}MoO{sub 4}{center_dot}2H{sub 2}O, MoO{sub 3}, Mo metal, and NH{sub 4}Cl produced (NH{submore » 4}){sub 7}[NaMo{sub 16}(OH){sub 12}O{sub 40}]{center_dot}4h{sub 2}O (1{center_dot}4H{sub 2}O) as red-orange crystals. The compound (Me{sub 3}NH){sub 4}K{sub 2}[H{sub 2}Mo{sub 16}(OH){sub 40}]{center_dot}8H{sub 2}O(2{center_dot}8H{sub 2}O(2{center_dot}8H{sub 2}O) was prepared in a similar fashion. The structure of the anion of 1 consists of an {epsilon}-Keggin core H{sub 12}Mo{sub 12}O{sub 40}, capped on four hexagonal faces by MoO{sub 3} units and encapsulating a Na{sup +} cation. The structure of the oxomolybdenum framework of 2 is essentially identical to that of 1; however, the central cavity is now occupied by 2H{sup +}.« less