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Title: Electron density analysis of the layered antiferromagnetic compound Cu{sub 2}(OH){sub 3}NO{sub 3}: Relationship with the magnetic interaction mechanism

Abstract

The electronic properties of the antiferromagnetic layer compound copper hydroxonitrate [Cu{sub 2}(OH){sub 3}NO{sub 3}] are investigated by high-resolution single-crystal x-ray diffraction at 114 K. A pseudoatomic multipolar model is used to reconstruct the experimental electron density (ED) distribution, whose quantitative analysis is performed through the quantum theory of atoms in molecules. The topological properties of the ED indicate indirect Cu{center_dot}{center_dot}{center_dot}Cu bonds mediated by the hydroxo and nitrate ions among the two-dimensional (2D) copper lattice. A mean charge transfer of 0.4 electrons from the copper atoms to the hydroxo groups and of 0.76 electrons to the nitrate ion is determined via numerical integration of the ED over the atomic basins. Low but nonetheless significant Cu-O partial covalent bonds do also exist. Interplane interaction pathways are furthermore localized and characterized.

Authors:
; ; ; ; ;  [1];  [2]
  1. Laboratoire de Cristallographie et Modelisation des Materiaux Mineraux et Biologiques, LCM3B, UMR CNRS 7036, Universite Henri Poincare, Nancy I, Faculte des sciences, Boite Postale 239, 54506 Vandoeuvre-les-Nancy (France)
  2. (France)
Publication Date:
OSTI Identifier:
20788002
Resource Type:
Journal Article
Resource Relation:
Journal Name: Physical Review. B, Condensed Matter and Materials Physics; Journal Volume: 73; Journal Issue: 11; Other Information: DOI: 10.1103/PhysRevB.73.115116; (c) 2006 The American Physical Society; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY; ANTIFERROMAGNETIC MATERIALS; ATOMS; CHEMICAL BONDS; COPPER; COPPER HYDROXIDES; COVALENCE; DISTRIBUTION; ELECTRON DENSITY; ELECTRON TRANSFER; ELECTRONS; EXCHANGE INTERACTIONS; IONS; LAYERS; MOLECULES; MONOCRYSTALS; NITRATES; TOPOLOGY; X-RAY DIFFRACTION

Citation Formats

Pillet, Sebastien, Souhassou, Mohamed, Lecomte, Claude, Rabu, Pierre, Drillon, Marc, Massobrio, Carlo, and Institut de Physique et Chimie des Materiaux de Strasbourg, 23 rue du Loess, 67037 Strasbourg. Electron density analysis of the layered antiferromagnetic compound Cu{sub 2}(OH){sub 3}NO{sub 3}: Relationship with the magnetic interaction mechanism. United States: N. p., 2006. Web. doi:10.1103/PHYSREVB.73.1.
Pillet, Sebastien, Souhassou, Mohamed, Lecomte, Claude, Rabu, Pierre, Drillon, Marc, Massobrio, Carlo, & Institut de Physique et Chimie des Materiaux de Strasbourg, 23 rue du Loess, 67037 Strasbourg. Electron density analysis of the layered antiferromagnetic compound Cu{sub 2}(OH){sub 3}NO{sub 3}: Relationship with the magnetic interaction mechanism. United States. doi:10.1103/PHYSREVB.73.1.
Pillet, Sebastien, Souhassou, Mohamed, Lecomte, Claude, Rabu, Pierre, Drillon, Marc, Massobrio, Carlo, and Institut de Physique et Chimie des Materiaux de Strasbourg, 23 rue du Loess, 67037 Strasbourg. Wed . "Electron density analysis of the layered antiferromagnetic compound Cu{sub 2}(OH){sub 3}NO{sub 3}: Relationship with the magnetic interaction mechanism". United States. doi:10.1103/PHYSREVB.73.1.
@article{osti_20788002,
title = {Electron density analysis of the layered antiferromagnetic compound Cu{sub 2}(OH){sub 3}NO{sub 3}: Relationship with the magnetic interaction mechanism},
author = {Pillet, Sebastien and Souhassou, Mohamed and Lecomte, Claude and Rabu, Pierre and Drillon, Marc and Massobrio, Carlo and Institut de Physique et Chimie des Materiaux de Strasbourg, 23 rue du Loess, 67037 Strasbourg},
abstractNote = {The electronic properties of the antiferromagnetic layer compound copper hydroxonitrate [Cu{sub 2}(OH){sub 3}NO{sub 3}] are investigated by high-resolution single-crystal x-ray diffraction at 114 K. A pseudoatomic multipolar model is used to reconstruct the experimental electron density (ED) distribution, whose quantitative analysis is performed through the quantum theory of atoms in molecules. The topological properties of the ED indicate indirect Cu{center_dot}{center_dot}{center_dot}Cu bonds mediated by the hydroxo and nitrate ions among the two-dimensional (2D) copper lattice. A mean charge transfer of 0.4 electrons from the copper atoms to the hydroxo groups and of 0.76 electrons to the nitrate ion is determined via numerical integration of the ED over the atomic basins. Low but nonetheless significant Cu-O partial covalent bonds do also exist. Interplane interaction pathways are furthermore localized and characterized.},
doi = {10.1103/PHYSREVB.73.1},
journal = {Physical Review. B, Condensed Matter and Materials Physics},
number = 11,
volume = 73,
place = {United States},
year = {Wed Mar 15 00:00:00 EST 2006},
month = {Wed Mar 15 00:00:00 EST 2006}
}
  • The syntheses of polynuclear copper(II)-lanthanide(III) complexes using the 2,6-bis[(dimethylamino)methyl]-4-methylphenolato ligand (bdmmp) have been investigated. The reaction of Cu(OCH{sub 3}){sub 2} with 2 equiv of bdmmpH in THF yields a mononuclear copper complex Cu(bdmmp){sub 2}(H{sub 2}O) (1), which subsequently reacts with 1 equiv of Pr(hfacac){sub 3} or La(O{sub 2}CCF{sub 3}){sub 3} (hfacac = hexafluoroacetylacetonato) to produce two heteronuclear complexes Pr{sup III}-Cu{sup II}(bdmmp)(bdmmpH)(OH)(hfacac){sub 3} (2) and [La{sup III}Cu{sup II}(bdmmp)(bdmmpH)(OH)(O{sub 2}CCF{sub 3}){sub 3}]{sub 2} (3). The reaction of Cu{sub 4}(bdmmp){sub 2}({mu}{sub 4}-O)(O{sub 2}CCF{sub 3}){sub 4} (4). The structures of compounds 1-4 have been determined by single-crystal X-ray diffraction analysis. The magnetic properties ofmore » these compounds have been examined by variable-temperature magnetic susceptibility measurements. The magnetism of compound 2 is dominated by the paramagnetism of the Pr(III) ion, while the magnetism of 4 is dominated by antiferromagnetic exchanges of the Cu(II) ions with J{sub 1} = -101 cm{sup {minus}1}, J{sub 2} = -101 cm{sup {minus}1}, J{sub 3} = -45 cm{sup {minus}1}, J{sub 4} = 3 cm{sup {minus}1}, and g = 2.02. UV-vis spectroscopic studies revealed that compound 1 has an intense ligand {yields} metal charge transfer band at {lambda} = 427 nm. Molecular orbital analysis on the electronic structure of 1 by extended Hueckel MO methods indicates that this absorption band is mainly due to the transitions of the {pi} orbitals of the phenoxy ligand to the singly occupied d{sub x{sup 2}-y{sup 2}} orbital of the copper ion.« less
  • The new compound Cu{sub 3}(TeO{sub 3}){sub 2}Br{sub 2} crystallizes in the monoclinic spacegroup C2/m. The unit cell parameters are a=9.3186(18)A, b=6.2781(9)A, c=8.1999(16)A, {beta}=107.39(2){sup o}, Z=2. The structure is solved from single crystal data, R{sub 1}=0.021. The new compound shows a layered structure where only weak van der Waals interactions connect the layers. There are two crystallographically different Cu(II) atoms; one having a square planar [CuO{sub 4}] coordination and one showing an unusual [CuO{sub 4}Br] trigonal bi-pyramidal coordination, the Br-ion is located in the equatorial plane. The Te(IV) atom has a tetrahedral [TeO{sub 3}E] coordination where E is the 5s{sup 2}more » lone-pair. Within the layers the Cu-polyhedra are connected by corner- and edge sharing to form chains. The chains are separated by the Te atoms. The magnetic properties are dominated by long range magnetic ordering at T{sub c}=70K. Evidence for a coexistence of ferromagnetic and antiferromagnetic interactions exists.« less
  • Single crystals of (NH{sub 3}(CH{sub 2}){sub 3}NH{sub 3})(H{sub 3}O){sub 2}(UO{sub 2}){sub 3}(MoO{sub 4}){sub 5} (1), C(NH{sub 2}){sub 3}(UO{sub 2})(OH)(MoO{sub 4}) (2), (C{sub 4}H{sub 12}N{sub 2})(UO{sub 2})(MoO{sub 4}){sub 2} (3) and (C{sub 5}H{sub 14}N{sub 2})(UO{sub 2})(MoO{sub 4}){sub 2}{center_dot}H{sub 2}O (4) have been synthesized hydrothermally by using UO{sub 2}(CH{sub 3}COO){sub 2}{center_dot}2H{sub 2}O, (NH{sub 4}){sub 2}Mo{sub 2}O{sub 7}, HF{sub (aq)}, H{sub 2}O, and the respective organic template. The materials have layered structures with anionic uranium molybdate sheets separated by cationic organic templates. Compound 1 has an unprecedented uranium molybdate topology, whereas 2 is structurally related to johannite, Cu[(UO{sub 2}){sub 2}(SO{sub 4}){sub 2}(OH){sub 2}](H{submore » 2}O){sub 8}, and 3 and f4 have layer topologies similar to zippiete, K{sub 2}[UO{sub 2}(MoO{sub 4}){sub 2}]. Thermogravimetric measurements indicate all that four materials, after template loss, form a crystalline mixture of UO{sub 2}MoO{sub 4} and MoO{sub 3}. Crystal data: (NH{sub 3}(CH{sub 2}){sub 3}(H{sub 3}O){sub 2}(UO{sub 2}){sub 3}(MoO{sub 4}){sub 5}, orthorhombic, space group Pbnm (No. 62), with a = 10.465(1) {angstrom}, b = 16.395(1) {angstrom}, c = 20.241(1) {angstrom}, and Z = 4; C(NH{sub 2}){sub 3}(UO{sub 2})(OH)MoO{sub 4}), monoclinic, space group P2{sub 1}/c (No. 14), with a = 15.411(1) {angstrom}, b = 7.086(1) {angstrom}, c = 18.108(1) {angstrom}, {beta} = 113.125(2){degree}, and Z = 4; (C{sub 4}H{sub 12}N{sub 2})(UO{sub 2})(MoO{sub 4}){sub 2}, triclinic, space group P{bar 1} (No. 2), with a = 7.096(1) {angstrom}, b = 8.388(1) {angstrom}, c = 11.634(1) {angstrom}, {alpha} = 97.008(3){degree}, {beta} = 96.454(2){degree}, {gamma} = 110.456(3){degree}, and Z = 2; (C{sub 5}H{sub 14}N{sub 2})(UO{sub 2})(MoO{sub 4}){sub 2}{center_dot}H{sub 2}O, orthorhombic, space group Pbca (No. 61), with a = 12.697(1) {angstrom}, b = 13.247(1) {angstrom}, c = 17.793(1) {angstrom}, and Z = 8.« less
  • A novel nanomolecular organic-inorganic hybrid compound, Na{sub 2}[NH(CH{sub 2}CH{sub 2}OH){sub 3}]{sub 4}{l_brace}Mo{sub 36}O{sub 112}(OH{sub 2}){sub 14} [OHCH{sub 2}CH{sub 2}NH(CH{sub 2}CH{sub 2}OH){sub 2}]{sub 2}{r_brace}.nH{sub 2}O (n{approx}72) (1), was synthesized in aqueous acidic medium with a high yield (85%) and characterized by single crystal X-ray crystallography, IR spectroscopy, {sup 1}H NMR, XRD and TG analysis. Compound 1 exhibits a supramolecular one-dimensional chainlike structure which consists of nanosized {l_brace}[Mo{sub 36}O{sub 112}(H{sub 2}O){sub 14}(HOC{sub 2}H{sub 4}){sub 2}NHC{sub 2}H{sub 4}OH]{sub 2}{r_brace}{sup 6-} anions ({l_brace}Mo{sub 36}(TEAH{sup +}){sub 2}{r_brace} for short) and cage-like dimers of TEAH{sup +} cations (TEAH{sup +}=protonated triethanolamine). In the {l_brace}Mo{sub 36}(TEAH{sup +}){sub 2}{r_brace}more » anion, two TEAH{sup +} cations connect to one ring-like {l_brace}[Mo{sub 36}O{sub 112}(H{sub 2}O){sub 16}]{sup 8-} ({l_brace}Mo{sub 36}{r_brace} for short) anion by covalent bonds via replacing two water ligands by the alkoxy ligands. The {l_brace}Mo{sub 36}(TEAH{sup +}){sub 2}{r_brace} unit could be considered as nanosized chelating ligand with [2N, 4O] donor sets. Crystal Data: triclinic, P-1, a=16.019(9) A, b=17.372(4) A, c=18.287(2) A, {alpha}=101.410(0){sup o}, {beta}=95.904(0){sup o}, {gamma}=116.332(0){sup o}, Z=1. - Graphical abstract: A novel organic-inorganic hybrid material based on macroisopolyanion {l_brace}Mo{sub 36}{r_brace} has been synthesized and characterized by X-ray single-crystal crystallography, XRD, IR spectroscopy, and TG analysis. The material exhibits a supramolecular one-dimensional chainlike structure. The {l_brace}Mo{sub 36}(TEAH{sup +}){sub 2}{r_brace} unit could be considered as nanosized chelating ligand with [2N, 4O] donor sets.« less