The crystal structure and magnetic properties of a new ferrimagnetic semiconductor: Ca21Mn4Sb18

Aaron P. Holm, Marilyn M. Olmstead, Susan M. Kauzlarich

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Abstract

Single crystals of the new transition metal Zintl phase, Ca21Mn4Sb18, were prepared by high temperature melt synthesis. The crystal structure was determined by single crystal X-ray diffraction to be monoclinic in the space group C2/c. Crystal information was obtained at 90 K, and unit cell parameters were determined (a = 17.100(2) Å, b = 17.073(2) Å, c = 16.857(2) Å, β = 92.999(2)°, Z = 2, R1 = 0.0540, wR2 = 0.1437). The structure can be described as containing 4 discreet units per formula unit: 1 linear [Mn4Sb10]22- anion, 2 dumbbell-shaped [Sb2]4- anions, 4 individual Sb3- anions, and 21 Ca2+ cations. The [Mn4Sb10]22- anion contains four edge-shared MnSb4 tetrahedra with distances between Mn ions of 3.388(4) Å, 2.782(4) Å, and 2.760(4) Å. Electron counting suggests that the Mn are 2+. Temperature dependent magnetization shows a ferromagnetic-like transition temperature at ∼52 K which is suppressed with increasing magnetic field. The paramagnetic regime is best fit to a ferrimagnetic model, providing a total effective moment of 4.04(2) μB, significantly less than that expected for 4 Mn2+ ions (11.8 μB). Temperature dependent resistivity shows that this compound is a semiconductor with an activation energy of 0.159(2) eV (100-300 K).

Original languageEnglish (US)
Pages (from-to)1973-1981
Number of pages9
JournalInorganic Chemistry
Volume42
Issue number6
DOIs
StatePublished - Mar 24 2003

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Anions
Magnetic properties
Crystal structure
Semiconductor materials
magnetic properties
anions
crystal structure
Single crystals
Ions
single crystals
tetrahedrons
Temperature
Transition metals
Cations
Magnetization
counting
ions
Activation energy
transition metals
transition temperature

ASJC Scopus subject areas

  • Inorganic Chemistry

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The crystal structure and magnetic properties of a new ferrimagnetic semiconductor : Ca21Mn4Sb18. / Holm, Aaron P.; Olmstead, Marilyn M.; Kauzlarich, Susan M.

In: Inorganic Chemistry, Vol. 42, No. 6, 24.03.2003, p. 1973-1981.

Research output: Contribution to journalArticle

Holm, Aaron P. ; Olmstead, Marilyn M. ; Kauzlarich, Susan M. / The crystal structure and magnetic properties of a new ferrimagnetic semiconductor : Ca21Mn4Sb18. In: Inorganic Chemistry. 2003 ; Vol. 42, No. 6. pp. 1973-1981.
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AB - Single crystals of the new transition metal Zintl phase, Ca21Mn4Sb18, were prepared by high temperature melt synthesis. The crystal structure was determined by single crystal X-ray diffraction to be monoclinic in the space group C2/c. Crystal information was obtained at 90 K, and unit cell parameters were determined (a = 17.100(2) Å, b = 17.073(2) Å, c = 16.857(2) Å, β = 92.999(2)°, Z = 2, R1 = 0.0540, wR2 = 0.1437). The structure can be described as containing 4 discreet units per formula unit: 1 linear [Mn4Sb10]22- anion, 2 dumbbell-shaped [Sb2]4- anions, 4 individual Sb3- anions, and 21 Ca2+ cations. The [Mn4Sb10]22- anion contains four edge-shared MnSb4 tetrahedra with distances between Mn ions of 3.388(4) Å, 2.782(4) Å, and 2.760(4) Å. Electron counting suggests that the Mn are 2+. Temperature dependent magnetization shows a ferromagnetic-like transition temperature at ∼52 K which is suppressed with increasing magnetic field. The paramagnetic regime is best fit to a ferrimagnetic model, providing a total effective moment of 4.04(2) μB, significantly less than that expected for 4 Mn2+ ions (11.8 μB). Temperature dependent resistivity shows that this compound is a semiconductor with an activation energy of 0.159(2) eV (100-300 K).

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