Synthesis, crystal and electronic structures and magnetic properties of Li2SnMo3O8: A novel reduced molybdenum oxide containing Mo3O13 cluster units

• The new quaternary reduced molybdenum oxide containing Mo3 clusters, Li2SnMo3O8, was synthesized by solid state reaction.
• Eight electrons per Mo3 cluster.
• Single-crystal X-ray study.
• Magnetic susceptibility measurements.
• Periodic density functional calculations.

Powder samples and single crystals of the quaternary oxide Li2SnMo3O8 were obtained by solid state reaction. The structure was determined by single-crystal X-ray diffraction. Li2SnMo3O8 crystallizes in the hexagonal space group P63mc with unit-cell parameters a=5.7720 (2) Å, c=10.3941 (3) Å and Z=2. Full-matrix least-squares refinement on F2 using 930 independent reflections for 31 refinable parameters results in R1=0.0354 and wR2=0.0643. 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-tin and molybdenum layers. The Li+ and Sn4+ 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 MoO6 octahedra that are each shared along two edges, constituting a Mo3O13 unit. Magnetic susceptibility measurements are in agreement with a spin-pairing of the eight d electrons per Mo3 cluster. The electronic structure of Li2SnMo3O8 is analyzed using periodic density functional calculations.

We present here the synthesis, the crystal and electronic structures, and the magnetic properties of the new quaternary compound containing Mo3O13 units, Li2SnMo3O8.Figure optionsDownload as PowerPoint slide