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Title: Crystal structure and magnetic properties of NaCu{sup II}[(Cu{sup II}{sub 3}O)(PO{sub 4}){sub 2}Cl]

Abstract

A new copper(II) oxide phosphate chloride, NaCu{sup II}[(Cu{sup II}{sub 3}O)(PO{sub 4}){sub 2}Cl], has been synthesized by flux synthesis. Single-crystal X-ray diffraction data show that the title compound crystallizes in the monoclinic system, space group P2{sub 1}/c (No. 14), with lattice parameters a=8.392(2) A, b=6.3960(10) A, c=16.670(2) A, {beta}=109.470(10) Degree-Sign , V=843.6(3) A{sup 3}, Z=4. The crystal structure is characterized by a complex chain of copper-centered polyhedra running along [0 1 0] which are connected by phosphate tetrahedra. The resulting three-dimensional polyhedra framework exhibits channels filled by additional copper and sodium atoms. Field and temperature dependent measurements of the specific heat and the magnetic susceptibility reveal low-dimensional magnetic behavior. The compound starts to decompose at 700 K under release of oxygen and evaporation of Cu{sup I}Cl as shown by simultaneous thermogravimetry and mass spectrometry. - Graphical abstract: The crystal structure of the new copper(II) phosphate chloride, NaCu{sup II}[(Cu{sup II}{sub 3}O)(PO{sub 4}){sub 2}Cl], exhibits linear chains of copper tetrahedra which show low-dimensional magnetic behavior proven by specific heat and magnetic susceptibility measurements. Highlights: Black-Right-Pointing-Pointer A new copper(II) oxide phosphate chloride, NaCu{sup II}[(Cu{sup II}{sub 3}O)(PO{sub 4}){sub 2}Cl], has been synthesized by flux synthesis. Black-Right-Pointing-Pointer The crystal structure comprises chains of Cu{sub 4}O tetrahedra.more » Black-Right-Pointing-Pointer Low-dimensional behavior has been proven by magnetic and specific heat measurements. Black-Right-Pointing-Pointer On heating, Cu{sup I}Cl and oxygen are released shown by simultaneous thermogravimetry and mass spectrometry.« less

Authors:
 [1];  [2]; ; ;  [3];  [1];  [3];  [3]
  1. Key Laboratory of Transparent Opto-Functional Inorganic Materials, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Dingxi Rd. 1295, Shanghai 200050 (China)
  2. Institute of Science and Engineering of Materials, Ocean University of China, Qingdao (China)
  3. Max-Planck-Institut fuer Chemische Physik fester Stoffe, Noethnitzer Str. 40, 01187 Dresden (Germany)
Publication Date:
OSTI Identifier:
22131099
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Solid State Chemistry; Journal Volume: 192; Other Information: Copyright (c) 2012 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; CHLORIDES; COPPER; COPPER OXIDES; FLUX SYNTHESIS; LATTICE PARAMETERS; MAGNETIC SUSCEPTIBILITY; MASS SPECTROSCOPY; MONOCLINIC LATTICES; MONOCRYSTALS; PHOSPHATES; SPACE GROUPS; SPECIFIC HEAT; TEMPERATURE DEPENDENCE; THERMAL GRAVIMETRIC ANALYSIS; X-RAY DIFFRACTION

Citation Formats

Jin Tengteng, Liu Wei, Chen Shuang, Prots, Yurii, Schnelle, Walter, Zhao Jingtai, Kniep, Ruediger, and Hoffmann, Stefan, E-mail: stefan.hoffmann@cpfs.mpg.de. Crystal structure and magnetic properties of NaCu{sup II}[(Cu{sup II}{sub 3}O)(PO{sub 4}){sub 2}Cl]. United States: N. p., 2012. Web. doi:10.1016/J.JSSC.2012.03.053.
Jin Tengteng, Liu Wei, Chen Shuang, Prots, Yurii, Schnelle, Walter, Zhao Jingtai, Kniep, Ruediger, & Hoffmann, Stefan, E-mail: stefan.hoffmann@cpfs.mpg.de. Crystal structure and magnetic properties of NaCu{sup II}[(Cu{sup II}{sub 3}O)(PO{sub 4}){sub 2}Cl]. United States. doi:10.1016/J.JSSC.2012.03.053.
Jin Tengteng, Liu Wei, Chen Shuang, Prots, Yurii, Schnelle, Walter, Zhao Jingtai, Kniep, Ruediger, and Hoffmann, Stefan, E-mail: stefan.hoffmann@cpfs.mpg.de. 2012. "Crystal structure and magnetic properties of NaCu{sup II}[(Cu{sup II}{sub 3}O)(PO{sub 4}){sub 2}Cl]". United States. doi:10.1016/J.JSSC.2012.03.053.
@article{osti_22131099,
title = {Crystal structure and magnetic properties of NaCu{sup II}[(Cu{sup II}{sub 3}O)(PO{sub 4}){sub 2}Cl]},
author = {Jin Tengteng and Liu Wei and Chen Shuang and Prots, Yurii and Schnelle, Walter and Zhao Jingtai and Kniep, Ruediger and Hoffmann, Stefan, E-mail: stefan.hoffmann@cpfs.mpg.de},
abstractNote = {A new copper(II) oxide phosphate chloride, NaCu{sup II}[(Cu{sup II}{sub 3}O)(PO{sub 4}){sub 2}Cl], has been synthesized by flux synthesis. Single-crystal X-ray diffraction data show that the title compound crystallizes in the monoclinic system, space group P2{sub 1}/c (No. 14), with lattice parameters a=8.392(2) A, b=6.3960(10) A, c=16.670(2) A, {beta}=109.470(10) Degree-Sign , V=843.6(3) A{sup 3}, Z=4. The crystal structure is characterized by a complex chain of copper-centered polyhedra running along [0 1 0] which are connected by phosphate tetrahedra. The resulting three-dimensional polyhedra framework exhibits channels filled by additional copper and sodium atoms. Field and temperature dependent measurements of the specific heat and the magnetic susceptibility reveal low-dimensional magnetic behavior. The compound starts to decompose at 700 K under release of oxygen and evaporation of Cu{sup I}Cl as shown by simultaneous thermogravimetry and mass spectrometry. - Graphical abstract: The crystal structure of the new copper(II) phosphate chloride, NaCu{sup II}[(Cu{sup II}{sub 3}O)(PO{sub 4}){sub 2}Cl], exhibits linear chains of copper tetrahedra which show low-dimensional magnetic behavior proven by specific heat and magnetic susceptibility measurements. Highlights: Black-Right-Pointing-Pointer A new copper(II) oxide phosphate chloride, NaCu{sup II}[(Cu{sup II}{sub 3}O)(PO{sub 4}){sub 2}Cl], has been synthesized by flux synthesis. Black-Right-Pointing-Pointer The crystal structure comprises chains of Cu{sub 4}O tetrahedra. Black-Right-Pointing-Pointer Low-dimensional behavior has been proven by magnetic and specific heat measurements. Black-Right-Pointing-Pointer On heating, Cu{sup I}Cl and oxygen are released shown by simultaneous thermogravimetry and mass spectrometry.},
doi = {10.1016/J.JSSC.2012.03.053},
journal = {Journal of Solid State Chemistry},
number = ,
volume = 192,
place = {United States},
year = 2012,
month = 8
}
  • The magnetic structure of a quasi-one-dimensional frustrated NaCu{sub 2}O{sub 2} magnet single crystal is studied by NMR. The spatial orientation of the planar spin spirals in the copper-oxygen Cu{sup 2+}-O chains is determined, and its evolution as a function of the applied magnetic field direction is analyzed.
  • Hydrothermal reaction of divalent metal chlorides with glutaric acid and 4,4'-dipyridylamine (dpa) has afforded an isostructural family of coordination polymers with formulation [M(glu)(dpa)]{sub n} (M=Co (1), Ni (2), Cu (3); glu=glutarate). Square pyramidal coordination is seen in 1-3, with semi-ligation of a sixth donor to produce a '5+1' extended coordination sphere. Neighboring metal atoms are linked into 1D [M(glu)]{sub n} neutral chains through chelating/monodentate bridging glutarate moieties with a syn-anti binding mode, and semi-chelation of the pendant carboxylate oxygen. These chains further connect into 2D layers through dipodal dpa ligands. Neighboring layers stack into the pseudo 3D crystal structure ofmore » 1-3 through supramolecular hydrogen bonding between dpa amine units and the semi-chelated glutarate oxygen atoms. The variable temperature magnetic behavior of 1-3 was explored and modeled as infinite 1D Heisenberg chains. Notably, complex 3 undergoes a thermally induced single crystal-to-single crystal transformation between centric and acentric space groups, with a conformationally disordered unilayer structure at 293 K and an ordered bilayer structure at 173 K. All materials were further characterized via infrared spectroscopy and elemental and thermogravimetric analyses. - Graphical abstract: The coordination polymers [M(glu)(dpa)]{sub n} (M=Co (1), Ni (2), Cu (3); glu=glutarate, dpa=4,4'-dipyridylamine) exhibit 2D layer structures based on 1D [M(glu)]{sub n} chains linked through dpa tethers. Antiferromagnetic coupling is observed for 2 and 3, while ferromagnetism is predominant in 1. Compound 3 undergoes a thermally induced single crystal-to-single crystal transformation from an acentric to a centrosymmetric space group.« less
  • Nickel was successfully introduced into the Gd{sub 5}Sb{sub 3} and Gd{sub 5}Bi{sub 3} binaries to yield the Gd{sub 5}Ni{sub 0.96(1)}Sb{sub 2.04(1)} and Gd{sub 5}Ni{sub 0.71(1)}Bi{sub 2.29(1)} phases. Both Ni-substituted compounds adopt the orthorhombic Yb{sub 5}Sb{sub 3}-type structure. While the Gd{sub 5}Ni{sub 0.71}Bi{sub 2.29} phase is thermodynamically stable at 800 deg. C and decomposes at lower temperatures upon annealing, it can be easily quenched to room temperature by rapid cooling from 800 deg. C. The Gd{sub 5}Ni{sub 0.96}Sb{sub 2.04} phase is found to be thermodynamically stable till room temperature. Through annealing at different temperatures, Gd{sub 5}Bi{sub 3} was proven to undergomore » the Mn{sub 5}Si{sub 3}-type (LT){r_reversible}Yb{sub 5}Sb{sub 3}-type (HT) transformation reversibly, whereas Gd{sub 5}Sb{sub 3} was found to adopt only the hexagonal Mn{sub 5}Si{sub 3}-type structure. Orthorhombic Gd{sub 5}Ni{sub 0.96}Sb{sub 2.04} and Gd{sub 5}Ni{sub 0.71}Bi{sub 2.29} and low-temperature hexagonal Gd{sub 5}Bi{sub 3} order ferromagnetically at 115, 162 and 112 K, respectively. In Gd{sub 5}Bi{sub 3}, the ferromagnetic ordering is followed by spin reorientation below 64 K. Magnetocaloric effect in terms of {delta}S was evaluated from the magnetization data and found to reach the maximum values of -7.7 J/kgK for Gd{sub 5}Ni{sub 0.96}Sb{sub 2.04} and -5.6 J/kgK for Gd{sub 5}Ni{sub 0.71}Bi{sub 2.29} around their Curie temperatures. - Graphical abstract: Ni substitution of Sb in Gd{sub 5}Sb{sub 3} and Gd{sub 5}Bi{sub 3} leads to the formation of the orthorhombic Yb{sub 5}Sb{sub 3}-type structure for Gd{sub 5}Ni{sub 0.96}Sb{sub 2.04} and stabilizes the orthorhombic bismuthide Gd{sub 5}Ni{sub 0.71}Bi{sub 2.29} to lower temperatures. Magnetic behavior and magnetocaloric effect was studied for hexagonal Mn{sub 5}Si{sub 3}-type Gd{sub 5}Bi{sub 3}, and orthorhombic Gd{sub 5}Ni{sub 0.96}Sb{sub 2.04} and Gd{sub 5}Ni{sub 0.71}Bi{sub 2.29}.« less
  • After crystals of CuNd{sub 2}Ge{sub 2}O{sub 8} are grown using CuO as self flux, the crystal structure is determined by single-crystal X-ray diffraction in the space group Cm (No. 8) to an R value of 5.1%. It is monoclinic, with a = 9.846(2){angstrom}, b=15.335(5) {angstrom}, c=8.336(1) {angstrom}, {beta}=148.48(2), V=657.9(5) {angstrom}{sub 3}, Z=4, and D{sub c}=6.31 g cm{sup -3}. CuNd{sub 2}Ge{sub 2}O{sub 8} shows a novel tridimensional structure type with chains of very distorted CuO{sub 6} octahedra, two kinds of coordinations for germanium (GeO{sub 5} trigonal bipyramids and rather regular GeO{sub 4} tetrahedra), and NdO{sub 8} triangulated dodecahedra. Above 100 Kmore » the reciprocal of the dc magnetic susceptibility of CuNd{sub 2}Ge{sub 2}O{sub 8} follows the Curie-Weiss law {chi}{sup -1} = 162(1)T+5971(93)g Oe/emu, with Weiss constant of spectra in the range 1000-100 cm{sup -1} are related to those of comparable species. The absorption spectrum at room temperature in the 350-7000 nm region is also given.« less
  • The grossly nonstoichiometric perovskites SrTiO{sub 3{minus}x} with x = 0.28, 0.17, and 0.08 were prepared from a reaction of Sr{sub 2}TiO{sub 4}, TiO, and TiO{sub 2} at 1,500{degree}C. For x = 0.28 relatively large single crystals were obtained. Also for this sample the crystal symmetry was found to depend on the rate of cooling from the reaction temperature and the annealing conditions. Rapidly cooled samples are tetragonal a = 3.9177(3) {angstrom}, c = 3.8878(5) {angstrom}. Samples annealed in vacuum at temperatures of 1,000 to 600{degree}C are cubic a = 3.9177(3) {angstrom}, c = 3.8878(5) {angstrom}. Samples annealed in vacuum atmore » temperatures of 1,000 to 600{degree}C are cubic a = 3.9075(3) {angstrom} with no change in cell volume. Single crystal data from a tetragonal sample indicate slight preferential occupancy of one oxygen position in P4/mmm. No evidence for any supercell due to defect ordering could be seen by TEM in either cubic or tetragonal samples. The x = 0.28 crystals show metallic resistivity, {rho}(300 K) = 6 {times} 10{sup {minus}4} ohm-cm and temperature-independent paramagnetism. {chi}{sub m} = 118 {times} 10{sup {minus}6} cm{sup 3} mole{sup {minus}1}. Hall effect data from 300 to 4.2 K analyzed on a single carrier model give a temperature-independent n-type carrier density of 2.4 {times} 10{sup 21} cm{sup {minus}3}.« less