Crystal Structure and Magnetic Properties of the Ba3TeCo3P2O14, Pb3TeCo3P2O14, and Pb3TeCo3V2O14 Langasites

TL;DR

This study investigates the crystal structures and magnetic properties of three langasite-related compounds, revealing complex distortions driven by Pb2+ lone pairs and their antiferromagnetic behavior with distinct Néel temperatures.

Contribution

It provides the first detailed structural and magnetic characterization of Ba3TeCo3P2O14, Pb3TeCo3P2O14, and Pb3TeCo3V2O14, highlighting the influence of Pb2+ lone pairs on structural distortion and magnetic properties.

Findings

Pb compounds exhibit complex structural distortions due to Pb2+ lone pairs.

All three compounds are antiferromagnetic with distinct Néel temperatures.

Magnetic behavior shows complexity at high magnetic fields.

Abstract

We report the structural and magnetic characterizations of Ba3TeCo3P2O14, Pb3TeCo3P2O14, and Pb3TeCo3V2O14, compounds that are based on the mineral Dugganite, which is isostructural to Langasites. The magnetic part of the structure consists of layers of Co2+ triangles. Nuclear and magnetic structures were determined through a co-refinement of synchrotron and neutron powder diffraction data. In contrast to the undistorted P321 Langasite structure of Ba3TeCo3P2O14, a complex structural distortion yielding a large supercell is found for both Pb3TeCo3P2O14 and Pb3TeCo3V2O14. Comparison of the three compounds studied along with the zinc analog Pb3TeZn3P2O14, also characterized here, suggests that the distortion is driven by Pb2+ lone pairs; as such, the Pb compounds crystallize in a pyroelectric space group, P2. Magnetic susceptibility, magnetization, and heat capacity measurements were performed to characterize the magnetic behavior. All three compounds become antiferromagnetic with N\'eel temperatures TN ~ 21 K (Ba3TeCo3P2O14), ~ 13 K (Pb3TeCo3P2O14), and ~ 8 K (Pb3TeCo3V2O14), and they exhibit magnetic transitions at high applied magnetic fields, suggesting intrinsically complex magnetic behavior for tetrahedrally coordinated d7 Co2+ in this structure type.