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Crystal structure and magnetic properties of two new cobalt selenite halides: Co5(SeO3)4X2 (X=Cl, Br)
Stockholm University, Faculty of Science, Department of Physical, Inorganic and Structural Chemistry.
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2007 (English)In: Journal of Solid State Chemistry, ISSN 0022-4596, E-ISSN 1095-726X, Vol. 180, no 3, 1051-1059 p.Article in journal (Refereed) Published
Abstract [en]

Two new isostructural cobalt selenite halides Co5(SeO3)4Cl2 and Co5(SeO3)4Br2 have been synthesized. They crystallize in the triclinic system space group P−1 with the following lattice parameters for Co5(SeO3)4Cl2: a=6.4935(8) Å, b=7.7288(8) Å, c=7.7443(10) Å, α=66.051(11)°, β=73.610(11)°, γ=81.268(9)°, and Z=1. The crystal structures were solved from single-crystal X-ray data, R1=3.73 and 4.03 for Co5(SeO3)4Cl2 and Co5(SeO3)4Br2, respectively. The new compounds are isostructural to Ni5(SeO3)4Br2.

Magnetic susceptibility measurements on oriented single-crystalline samples show anisotropic response in a broad temperature range. The anisotropic susceptibility is quantitatively interpreted within the zero-field splitting schemes for Co2+ and Ni2+ ions. Sharp low-temperature susceptibility features, at TN=18 and 20 K for Co5(SeO3)4Cl2 and Co5(SeO3)4Br2, respectively, are ascribed to antiferromagnetic ordering in a minority magnetic subsystem. In isostructural Ni5(SeO3)4Br2 magnetically ordered subsystem represents a majority fraction (TN=46 K). Nevertheless, anisotropic susceptibility of Ni5(SeO3)4Br2 is dominated at low temperatures by a minority fraction, subject to single-ion anisotropy effects and increasing population of Sz=0 (singlet) ground state of octahedrally coordinated Ni2+.

Place, publisher, year, edition, pages
2007. Vol. 180, no 3, 1051-1059 p.
Keyword [en]
Oxo-halide, Lone-pair elements, Crystal structure determination, Magnetic susceptibility, Zero-field splitting, Single-ion anisotropy
National Category
Chemical Sciences
URN: urn:nbn:se:su:diva-23091DOI: 10.1016/j.jssc.2006.12.035OAI: diva2:190061
Available from: 2007-01-02 Created: 2007-01-02 Last updated: 2011-02-16Bibliographically approved
In thesis
1. Terminating species and Lewis acid-base preference in oxohalides – a new route to low-dimensional compounds
Open this publication in new window or tab >>Terminating species and Lewis acid-base preference in oxohalides – a new route to low-dimensional compounds
2007 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

This thesis is based upon synthesis and structure determination of new transition metal oxo-halide compounds, which includes p-element cations that have a stereochemically active lone pair. A synthesis concept has been developed, which uses several different structural features to increase the possibility to yield a low-dimensional arrangement of transition metal cations. A total of 17 new compounds has been synthesised and their structures have been determined via single-crystal X-ray diffraction. The halides and the stereochemically active lone-pairs will typically act as terminating species segregating into regions of non-bonding volumes, which may take the form of 2D layers, 1D channels or Euclidean spheres. The transition metals that have been used for this work are copper, cobalt and iron. The Hard-Soft-Acid-Base principle has been utilized to match strong Lewis acids to strong Lewis bases and weak acids to weak bases. All compounds show tendencies towards low-dimensionality; they all have sheets of transition metal cations arranged into layers, where the layers most often are connected via weak dispersion forces.

Place, publisher, year, edition, pages
Stockholm: Institutionen för fysikalisk kemi, oorganisk kemi och strukturkemi, 2007. 174 p.
Low dimensionality, crystal structures, tellurites, selenites, oxohalides
National Category
Inorganic Chemistry
urn:nbn:se:su:diva-1414 (URN)91-7155-365-7 (ISBN)
Public defence
2007-02-02, Magnélisalen, Kemiska övningslaboratoriet, Svante Arrhenius väg 12 A, Stockholm, 10:00
Available from: 2007-01-02 Created: 2007-01-02Bibliographically approved

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