Ca{sub 4}Fe{sub 3-x}Mn{sub x}O{sub 8-{delta}C}l{sub 2}: A new n=3 Ruddlesden-Popper oxychloride

Journal Article · Tue Jun 15 00:00:00 EDT 2010 · Journal of Solid State Chemistry

DOI:https://doi.org/10.1016/j.jssc.2010.03.019· OSTI ID:21421503

Tao, Yang ^[1]; Junliang, Sun ^[2]; Croft, Mark ^[3]; Nowik, Israel ^[4]; Ignatov, Alexander ^[5]; Rihong, Cong ^[6]; Greenblatt, Martha ^[1]

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1. Department of Chemistry and Chemical Biology, Rutgers, State University of New Jersey, 610 Taylor Road, Piscataway, NJ 08854-8087 (United States)
2. Structural Chemistry, Stockholm University, SE-10691 Stockholm (Sweden)
3. Department of Physics and Astronomy, Rutgers, State University of New Jersey, 136 Frelinghuysen Road, Piscataway, NJ 08854 (United States)
4. Racah Institute of Physics, Hebrew University, Jerusalem 91904 (Israel)
5. Materials Science and Engineering Department, Rutgers University, Piscataway, NJ 08854 (United States)
6. College of Chemistry and Molecular Engineering, Peking University, Beijing 100871 (China)

Solid state solutions of Ca{sub 4}Fe{sub 3-x}Mn{sub x}O{sub 8-{delta}C}l{sub 2} (0.92{<=}x{<=}1.79 ({delta}{approx}0.1) single crystals were synthesized in CaCl{sub 2}-flux in air. The structure, determined by single-crystal X-ray diffraction, is related to the n=3 Ruddlesden-Popper phase in space group I4/mmm with strong deviations from the ideal structure. Mn and Fe are disordered over two transition metal sites. Due to the positional disordering of the equatorial oxygen atoms in the MO{sub 6} octahedra in Ca{sub 4}Fe{sub 3-x}Mn{sub x}O{sub 8-{delta}C}l{sub 2} both tilting ({approx}9{sup o}) along the c-axis and rotation ({approx}10.5{sup o}) within the ab-plane are observed. All the Fe ions are trivalent, as confirmed by {sup 57}Fe Moessbauer spectroscopy and X-ray absorption near edge spectroscopy (XAS), while the formal valence state of Mn varies from very close to 4+ in the x=0.92 to mix-valent 3+/4+ in the x=1.79 member, as indicated by XAS. Magnetic investigations evidence short-range antiferromagnetic ordering already at room temperature and spin-glass behavior at low temperature due to the structural disordering of Mn/Fe. - Graphical abstract: Structural analysis by the X-ray diffraction, the {sup 57}Fe Moessbauer and the X-ray absorption spectroscopy shows that all Fe ions are trivalent, the valence of Mn varies from {approx}4+ to 3+/4+ with increasing x.

• OSTI ID: 21421503
• Journal Information: Journal of Solid State Chemistry, Vol. 183, Issue 6; Other Information: DOI: 10.1016/j.jssc.2010.03.019; PII: S0022-4596(10)00109-X; Copyright (c) 2010 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved.; ISSN 0022-4596
• Country of Publication: United States
• Language: English

Related Subjects

36 MATERIALS SCIENCE
ABSORPTION
ABSORPTION SPECTROSCOPY
ANTIFERROMAGNETISM
CALCIUM CHLORIDES
CALCIUM COMPOUNDS
IRON 57
IRON COMPOUNDS
IRON IONS
MANGANESE COMPOUNDS
MOESSBAUER EFFECT
MONOCRYSTALS
OXYCHLORIDES
SOLUTIONS
SPACE GROUPS
SPIN GLASS STATE
TEMPERATURE RANGE 0273-0400 K
TETRAGONAL LATTICES
X-RAY DIFFRACTION
X-RAY SPECTROSCOPY
ALKALINE EARTH METAL COMPOUNDS
CALCIUM HALIDES
CHARGED PARTICLES
CHLORIDES
CHLORINE COMPOUNDS
COHERENT SCATTERING
CRYSTAL LATTICES
CRYSTAL STRUCTURE
CRYSTALS
DIFFRACTION
DISPERSIONS
EVEN-ODD NUCLEI
HALIDES
HALOGEN COMPOUNDS
HOMOGENEOUS MIXTURES
INTERMEDIATE MASS NUCLEI
IONS
IRON ISOTOPES
ISOTOPES
MAGNETISM
MIXTURES
NUCLEI
OXYGEN COMPOUNDS
OXYHALIDES
SCATTERING
SORPTION
SPECTROSCOPY
STABLE ISOTOPES
SYMMETRY GROUPS
TEMPERATURE RANGE
TRANSITION ELEMENT COMPOUNDS