Crystal Structure and Vibrational Properties of a Sodium Oxoferrate(II) Hydroxide, Na<sub>5</sub>[FeO<sub>3</sub>][OH]

Gheorghe, Dana E.; Litvinchuk, A. P.; Möller, Angela

doi:10.1002/zaac.201200178

Cited by 4 publications

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“…The red shift of the stronger IR-mode (tentatively assigned to an out-of-phase displacement) is often taken as an indicator for hydrogen bonding . In comparison, typical “free” OH – ions exhibit vibrations around 3556 cm –1 . , Considering the geometric information (Table ) and the relative red shift, Δν(O–H) ≈ −67 cm –1 , the interaction between the proton of the hydroxide and vanadate is thus weak and dominantly of electrostatic origin. The higher-frequency ν(O–H) mode is detected also in the RA spectrum and consequently assigned to an in-phase displacement.…”

Section: Resultsmentioning

confidence: 99%

BaMn₉[VO₄]₆(OH)₂: A Unique Canted Antiferromagnet with a Chiral “Paddle-Wheel” Structural Feature

et al. 2014

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BaMn(9)[VO(4)](6)(OH)(2) was synthesized by hydrothermal methods. We evaluated the crystal structure based on the two possible space groups P2(1)3 and Pa3̅ [a = 12.8417(2) Å] using single-crystal and powder X-ray diffraction techniques. The structure contains three-dimensionally linked Mn(9) units of a chiral "paddle-wheel" type. Experimental IR and Raman spectra were analyzed in terms of fundamental vanadate and hydroxide vibrational modes. The magnetic properties were investigated, and the specific heat in applied fields was studied. The dominant magnetic interactions (Mn(2+), S = 5/2) are of antiferromagnetic origin, as indicated by a Curie-Weiss fit above 175 K with Θ ≈ -200 K. Canting of the spins on the geometrically frustrated triangle segment of the structural feature is considered to account for the ferrimagnetic type of long-range order at T(C) ≈ 18 K. We propose a model for the spin structure in the ordered regime. Dielectric constants were measured and indicate a magnetodielectric effect at T(C), which is assigned to spin-lattice coupling.

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Section: Resultsmentioning

confidence: 99%

BaMn₉[VO₄]₆(OH)₂: A Unique Canted Antiferromagnet with a Chiral “Paddle-Wheel” Structural Feature

et al. 2014

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“…While a broad variety of alkali metal oxoferrates(III) was described, such as A FeO 2 ( A =K, Rb, Cs), A 4 Fe 2 O 5 ( A =Na, K), K 14 Fe 4 O 13 , K 17 Fe 5 O 16 or K 6 Fe 2 O 6 , quaternary alkali metal oxohydroxoferrates(III) were up to now unknown. The oxoferrate(II) hydroxide Na 5 [FeO 3 ]OH contains iron(II) in trigonal [FeO 3 ] 4− units and “isolated” hydroxide ions . With alkaline earth metals, the oxoferrate(II,III) hydroxoferrate(III) Ba 4 [Fe 8 O 14 ][Fe(OH) 6 ] and the perovskite Ba[FeO 2.5−x (OH) 2x ], were described.…”

Section: Introductionmentioning

confidence: 99%

Antiferromagnetic Alkali Metal Oxohydroxoferrates(III) with Correlated Hydrogen Bonding Systems

et al. 2019

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The oxohydroxoferrates(III) A 2 [Fe 2 O 3 (OH) 2 ] (A = K, Rb, Cs) were synthesized under hydroflux conditions. Approximately equimolar mixtures of the alkali metal hydroxides and water were reacted with Fe(NO 3 ) 3 · 9H 2 O at about 200°C. The product formation depends on the hydroxide concentration, therefore also other reaction products, such as KFeO 2 , K 2À x [Fe 4 O 7À x (OH) x ] or α-Fe 2 O 3 , are obtained. The crystal structures of the oxohydroxoferrates(III) A 2 [Fe 2 O 3 (OH) 2 ] follow the same structural principle, yet differ in their layer stacking or/and their hydrogen bonding systems depending on A and temperature. In the resulting four different orthorhombic structure types, [FeO 3 OH] 4À tetrahedra share their oxide corners to create folded 1 2 ½Fe 2 O 3 (OH) 2 ] 2À layers. The terminal hydroxide ligands form hydrogen bonds between and/or within the layers. The positions of the hydrogen atoms in these networks are correlated. The A + cations are located between the folded anionic layers as well as in their trenches. Under reaction conditions, the potassium compound crystallizes in the space group Cmce (Pearson symbol oC88), showing a bimodal disorder of the hydrogen atoms in hydrogen bridges. In a virtually hysteresis-less first-order transition at 340(2) K, the structure slightly distorts into the room-temperature modification with the subgroup Pbca (oP88), and the hydrogen atoms order. The rubidium and caesium compounds are isostructural to each other but not to the potassium compound, and are always obtained as mixtures of two modifications with space groups Cmce (oC88') and Immb (oI88). Upon heating, the oxohydroxoferrates decompose into their anhydrides AFeO 2 and water. The type of hydrogen bonding network influences the decomposition temperature, the structure and the morphology of the crystals. Despite the presence of iron(III), which was confirmed by 57 Fe-Mössbauer spectroscopy, K 2 [Fe 2 O 3 (OH) 2 ] is diamagnetic in the investigated temperature range between 1.8 and 300 K. Neutron diffraction revealed strong antiferromagnetic coupling of the magnetic moments, which are inverted in neighboring tetrahedra.

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ChemInform Abstract: Crystal Structure and Vibrational Properties of a Sodium Oxoferrate(II) Hydroxide, Na₅[FeO₃][OH].

2013

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Crystal Structure and Vibrational Properties of a Sodium Oxoferrate(II) Hydroxide, Na5[FeO3][OH]. -Red crystals of the title compound are prepared by reaction of Na2O, Fe, CdO, and NaOH (Ag container, argon, 450°C, 5 d). The compound is characterized by single crystal XRD and single crystal IR and Raman spectroscopy. Na5[FeO3][OH] crystallizes in the space group Pnma with Z = 8. Aspects of the isolated [FeO 3 ] 4complexes and non-coordinating hydroxide in comparison with the respective cobalt compounds are discussed. -(GHEORGHE, D. E.; LITVINCHUK, A. P.; MOELLER*, A.

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Crystal Structure and Vibrational Properties of a Sodium Oxoferrate(II) Hydroxide, Na₅[FeO₃][OH]

Cited by 4 publications

References 32 publications

BaMn₉[VO₄]₆(OH)₂: A Unique Canted Antiferromagnet with a Chiral “Paddle-Wheel” Structural Feature

BaMn₉[VO₄]₆(OH)₂: A Unique Canted Antiferromagnet with a Chiral “Paddle-Wheel” Structural Feature

Antiferromagnetic Alkali Metal Oxohydroxoferrates(III) with Correlated Hydrogen Bonding Systems

ChemInform Abstract: Crystal Structure and Vibrational Properties of a Sodium Oxoferrate(II) Hydroxide, Na₅[FeO₃][OH].

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Crystal Structure and Vibrational Properties of a Sodium Oxoferrate(II) Hydroxide, Na5[FeO3][OH]

Cited by 4 publications

References 32 publications

BaMn9[VO4]6(OH)2: A Unique Canted Antiferromagnet with a Chiral “Paddle-Wheel” Structural Feature

BaMn9[VO4]6(OH)2: A Unique Canted Antiferromagnet with a Chiral “Paddle-Wheel” Structural Feature

Antiferromagnetic Alkali Metal Oxohydroxoferrates(III) with Correlated Hydrogen Bonding Systems

ChemInform Abstract: Crystal Structure and Vibrational Properties of a Sodium Oxoferrate(II) Hydroxide, Na5[FeO3][OH].

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Crystal Structure and Vibrational Properties of a Sodium Oxoferrate(II) Hydroxide, Na₅[FeO₃][OH]

BaMn₉[VO₄]₆(OH)₂: A Unique Canted Antiferromagnet with a Chiral “Paddle-Wheel” Structural Feature

BaMn₉[VO₄]₆(OH)₂: A Unique Canted Antiferromagnet with a Chiral “Paddle-Wheel” Structural Feature

ChemInform Abstract: Crystal Structure and Vibrational Properties of a Sodium Oxoferrate(II) Hydroxide, Na₅[FeO₃][OH].