Synthesis, crystal structure and magnetic properties of Li{sub 2}InMo{sub 3}O{sub 8}: A novel reduced molybdenum oxide containing magnetic Mo{sub 3} clusters
Powder samples and single crystals of Li{sub 2}InMo{sub 3}O{sub 8} were obtained by solid state reaction. The structure was determined by single-crystal X-ray diffraction (771 independent reflections for 33 refinable, R1=0.0158 and wR2=0.0354). Li{sub 2}InMo{sub 3}O{sub 8} is isomorphous with Li{sub 2}SnMo{sub 3}O{sub 8} and crystallizes in the hexagonal space group P6{sub 3}mc with unit-cell parameters a=5.7931(2) Å, c=10.4681(4) Å and Z=2. The crystal structure consists of distorted hexagonal-close-packed oxygen layers with stacking sequence abac along [0 0 1] and that are held together by alternating lithium–indium and molybdenum layers. The Li{sup +} and In{sup 3+} ions occupy, respectively, tetrahedral and octahedral sites in the ratio 2:1. The Mo atoms occupy octahedral sites and form strongly bonded triangular clusters involving three MoO{sub 6} octahedra that are each shared along two edges, constituting a Mo{sub 3}O{sub 13} unit. The variations of the Mo–Mo and Mo–O bond lengths according to the number of electrons per Mo{sub 3} cluster are discussed. The trivalent oxidation state of the indium leads to one unpaired electron per Mo{sub 3} and thus gives rise to a paramagnetic spin behavior with an effective magnetic moment of 1.5 μ{sub B} per Mo{sub 3} cluster. The magnetic susceptibility vs. temperature curve also shows a maximum at 25 K arising probably from an antiferromagnetic ordering between the Mo{sub 3} clusters. - Graphical abstract: We present here the synthesis, the crystal structure, and the magnetic properties of the new quaternary compound Li{sub 2}InMo{sub 3}O{sub 8} containing magnetic Mo{sub 3}O{sub 13} units with one unpaired electron. - Highlights: • The new quaternary reduced molybdenum oxide containing Mo{sub 3} clusters, Li{sub 2}InMo{sub 3}O{sub 8}, was synthesized by solid state reaction. • Single-crystal X-ray study. • One unpaired electron per Mo{sub 3} cluster leading to a paramagnetic spin behavior with an effective magnetic moment of 1.5 μ{sub B} per Mo{sub 3} cluster. • Magnetic susceptibility measurements show a maximum at 25 K arising probably from an antiferromagnetic ordering between the Mo{sub 3} clusters.
- OSTI ID:
- 22309072
- Journal Information:
- Journal of Solid State Chemistry, Vol. 208; Other Information: Copyright (c) 2013 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved.; Country of input: International Atomic Energy Agency (IAEA); ISSN 0022-4596
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
ANTIFERROMAGNETISM
BOND LENGTHS
HCP LATTICES
INDIUM IONS
LITHIUM IONS
MAGNETIC MOMENTS
MAGNETIC SUSCEPTIBILITY
MOLYBDENUM
MOLYBDENUM OXIDES
MONOCRYSTALS
PARAMAGNETISM
QUATERNARY ALLOY SYSTEMS
QUATERNARY AMMONIUM COMPOUNDS
SPACE GROUPS
SPIN
SYNTHESIS
X RADIATION
X-RAY DIFFRACTION