skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Synthesis, Crystal Structure, and Properties of the Rhomboheral Modification of the Thiospinel CuZr1.86(1)S4

Abstract

The rhombohedral modification of the thiospinel, CuZr{sub 1.86(1)}S{sub 4}, has been synthesized by the reaction of the constituent elements in an alkali metal halide flux and structurally characterized by single crystal X-ray diffraction techniques. The title compound crystallizes in the rhombohedral space group D{sub 3d}{sup 5}-R{bar 3}m (166, a=7.3552(2) {angstrom}, c=35.832(2) {angstrom}, V=1678.76(13) {angstrom}{sup 3}, Z=12, and R/wR=0.0239/0.0624). The structure is composed of close packed S layers, with a stacking order of ABCBCABABCACAB along the c axis. The Zr and Cu atoms occupy the octahedral and tetrahedral holes between S layers, respectively. Three different kinds of S-M-S layers exist in the structure: layer I has fully occupied Zr and Cu sites, layer II has fully occupied Zr sites but no Cu, and layer III has partially occupied Zr and fully occupied Cu sites. Transport and optical properties indicate that the title compound is a small band gap (1.26 eV) n-type semiconductor.

Authors:
 [1];  [2];  [3];  [1]
  1. Cornell University
  2. ORNL
  3. Ajou University, Suwon, South Korea
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
973547
DOE Contract Number:
DE-AC05-00OR22725
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Solid State Chemistry; Journal Volume: 183; Journal Issue: 3
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; ALKALI METALS; ATOMS; CRYSTAL STRUCTURE; HALIDES; MODIFICATIONS; MONOCRYSTALS; OPTICAL PROPERTIES; SPACE GROUPS; SYNTHESIS; TRANSPORT; X-RAY DIFFRACTION

Citation Formats

Dong, Yongkwan, McGuire, Michael A, Hoseop, Yun, and DiSalvo, Francis J. Synthesis, Crystal Structure, and Properties of the Rhomboheral Modification of the Thiospinel CuZr1.86(1)S4. United States: N. p., 2009. Web.
Dong, Yongkwan, McGuire, Michael A, Hoseop, Yun, & DiSalvo, Francis J. Synthesis, Crystal Structure, and Properties of the Rhomboheral Modification of the Thiospinel CuZr1.86(1)S4. United States.
Dong, Yongkwan, McGuire, Michael A, Hoseop, Yun, and DiSalvo, Francis J. Thu . "Synthesis, Crystal Structure, and Properties of the Rhomboheral Modification of the Thiospinel CuZr1.86(1)S4". United States. doi:.
@article{osti_973547,
title = {Synthesis, Crystal Structure, and Properties of the Rhomboheral Modification of the Thiospinel CuZr1.86(1)S4},
author = {Dong, Yongkwan and McGuire, Michael A and Hoseop, Yun and DiSalvo, Francis J.},
abstractNote = {The rhombohedral modification of the thiospinel, CuZr{sub 1.86(1)}S{sub 4}, has been synthesized by the reaction of the constituent elements in an alkali metal halide flux and structurally characterized by single crystal X-ray diffraction techniques. The title compound crystallizes in the rhombohedral space group D{sub 3d}{sup 5}-R{bar 3}m (166, a=7.3552(2) {angstrom}, c=35.832(2) {angstrom}, V=1678.76(13) {angstrom}{sup 3}, Z=12, and R/wR=0.0239/0.0624). The structure is composed of close packed S layers, with a stacking order of ABCBCABABCACAB along the c axis. The Zr and Cu atoms occupy the octahedral and tetrahedral holes between S layers, respectively. Three different kinds of S-M-S layers exist in the structure: layer I has fully occupied Zr and Cu sites, layer II has fully occupied Zr sites but no Cu, and layer III has partially occupied Zr and fully occupied Cu sites. Transport and optical properties indicate that the title compound is a small band gap (1.26 eV) n-type semiconductor.},
doi = {},
journal = {Journal of Solid State Chemistry},
number = 3,
volume = 183,
place = {United States},
year = {Thu Jan 01 00:00:00 EST 2009},
month = {Thu Jan 01 00:00:00 EST 2009}
}
  • The rhombohedral modification of the thiospinel, CuZr{sub 1.86(1)}S{sub 4}, has been synthesized by the reaction of the constituent elements in an alkali metal halide flux and structurally characterized by single crystal X-ray diffraction techniques. The title compound crystallizes in the rhombohedral space group D{sub 3d}{sup 5}-R3-barm (no. 166, a=7.3552(2) A, c=35.832(2) A, V=1678.76(13) A{sup 3}, Z=12, and R/wR=0.0239/0.0624). The structure is composed of close packed S layers, with a stacking order of ...ABCBCABABCACAB....along the c axis. The Zr and Cu atoms occupy the octahedral and tetrahedral holes between S layers, respectively. Three different kinds of S-M-S layers exist in themore » structure: layer I has fully occupied Zr and Cu sites, layer II has fully occupied Zr sites but no Cu, and layer III has partially occupied Zr and fully occupied Cu sites. Transport and optical properties indicate that the title compound is a small band gap (1.26 eV) n-type semiconductor. - Graphical abstract: The projected view of the rhombohedral modification, CuZr{sub 1.86(1)}S{sub 4}, down the [100] direction. Large letters denote the packing sequence of the S atoms (yellow circles) along the c axis. Zr (black circles) and Cu (red circles) atoms occupy the octahedral and tetrahedral holes, respectively, between close packed S layers.« less
  • The influence of Zn-doping on the crystal structure and magnetic properties of the spin ladder compounds La{sub 2}Cu{sub 2}O{sub 5} (4-leg) and La{sub 8}Cu{sub 7}O{sub 19} (5-leg) have been investigated. The La{sub 2}(Cu{sub 1-x}Zn{sub x}){sub 2}O{sub 5} and La{sub 8}(Cu{sub 1-x}Zn{sub x}){sub 7}O{sub 19} solid solutions were obtained as single phases with x=0-0.1 via the solid-state reaction method in the temperature range between 1005-1010 deg. C and 1015-1030 deg. C in oxygen and air atmospheres, respectively. The lattice parameters a and c of the monoclinic crystal structures as well as the unit cell volume V increase with increasing x, whilemore » b and {beta} decrease for both series. The magnetic susceptibilities {chi} of both series show a very similar behavior on temperature as well as on Zn-doping, which is supposed to be due to the similar Cu-O coordination in both La{sub 2}Cu{sub 2}O{sub 5} and La{sub 8}Cu{sub 7}O{sub 19}. For low Zn-doping (x=<0.04), a spin-chain like behavior is found. This quasi-one-dimensional behavior is strongly suppressed in both series for x>=0.04. Here, the maximum (characteristic for spin chains) in {chi}(T) disappears and {chi}(T) decreases monotonically with increasing temperature.« less
  • To prepare new mesogenic materials, the dinuclear palladium(II) complexes (Pd(L)({mu}-Cl)){sub 2} have been synthesized by cyclometalation of the HLn species (HLn = 5-R-2-4({prime}-R{prime}-phenyl)pyrimidine; HL1, R = C{sub 6}H{sub 13}, R{prime} = CH{sub 3}; HL2, R = C{sub 9}H{sub 19}, R{prime} = CH{sub 3}; HL3, R = C{sub 6}H{sub 13}, R{prime} = C{sub 11}H{sub 23}; HL4: R = C{sub 9}H{sub 19}). With these complexes as precursors, a number of (Pd(L)({mu}-X)){sub 2} compounds (X = Cl, Br, I, OAc) have been obtained by metathetical reactions. The molecular structure of (Pd(L1)({mu}-OAc)){sub 2} has been determined by a single-crystal X-ray analysis. The crystals aremore » triclinic, space group P1 with Z = 2. Unit cell parameters are a = 10.454 (1) {angstrom}, b = 13.229 (1) {angstrom}, c = 14.674 (2) {angstrom}, {alpha} = 80.20 (1){degree}, {beta} = 79.97 (1){degree}, {gamma} = 72.87 (1){degree}, V = 1894.5 (4) {angstrom}{sup 3}, D(calcd) = 1.36 g cm{sup {minus}3} for mol wt 869.62.« less
  • The alkaline-earth metal vanadium(IV) oxide system with formula (Ca{sub 1{minus}x}Sr{sub x})VO{sub 3} has been synthesized using the metallo-organic method. The oxides prepared at temperatures of 1,073--1,173 K showed the presence of an oxygen excess while those obtained at higher temperatures (1,273 K) were found to be stoichiometric. The crystal structure of these oxides (stoichiometric and non-stoichiometric) is perovskite with different symmetry depending on the strontium substitution: orthorhombic (0 {le} x {le} 0.2), tetragonal (0.3 {le} x {le} 0.4), and cubic (0.75 {le} x {le} x). The influence of strontium substitution on the [VO{sub 6}] groups symmetry was also observed bymore » vibrational spectroscopy. The electrical properties of the oxides are not extensively influenced by the stoichiometry and cation substitution.« less