Crystal Structure Refinement and Magnetic Properties of Fe 4(P 2O 7) 3 Studied by Neutron Diffraction and Mössbauer Techniques
Abstract
Fe4(P2O7)3 was prepared from Fe(PO3)3 and FePO4 at 940°C under oxygen. The unit cell is monoclinic, space group P21/n, with a=7.389(2) Å, b=21.337(1) Å, c=9.517(2) Å, β=90(1)°, and Z=4. The crystallographic structure has been determined from a single crystal through direct methods and difference Fourier synthesis and refined to R=0.10 (Rw=0.09). The three-dimensional framework is built up from Fe2O9 clusters of two face-sharing octahedra, linked by bent diphosphates P2O7 (P-O-P∼156°). Fe4(P2O7)3 is antiferromagnetic below TN=50 K. The magnetic structure has been determinated by means of powder neutron diffraction. There are four antiferromagnetic iron sublattices corresponding to the four crystallographically distinct iron atoms. The magnetic moments are antiferromagnetically coupled inside the Fe2O9 dimers, in agreement with the Goodenough rules. They are parallel to the c axis and have 4.55(5) μB value at 1.7 K. The magnetic interactions are discussed. Mössbauer spectra are fitted with four doublets and sextuplets in the paramagnetic and antiferromagnetic states, respectively. Their rather high isomer shifts are explained by the inductive effect.
- Publication:
-
Journal of Solid State Chemistry France
- Pub Date:
- February 2002
- DOI:
- 10.1006/jssc.2001.9415
- Bibcode:
- 2002JSSCh.163..412E
- Keywords:
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- iron phosphate;
- single crystal;
- crystal structure;
- magnetic structure;
- <SUP>57</SUP>Fe Mössbauer spectrometry.