TY - JOUR
T1 - The flexible Ba7UM2S12.5O0.5 (M = V, Fe) compounds
T2 - Syntheses, structures and spectroscopic, resistivity, and electronic properties
AU - Mesbah, Adel
AU - Stojko, Wojciech
AU - Malliakas, Christos D.
AU - Lebègue, Sébastien
AU - Clavier, Nicolas
AU - Ibers, James A.
PY - 2013/10/21
Y1 - 2013/10/21
N2 - Two new compounds, Ba7UV2S12.5O 0.5 and Ba7UFe2S12.5O0.5, have been synthesized in fused-silica tubes by the direct combinations of V or Fe with U, BaS, and S at 1223 K. The compound Ba7UV2S 12.5O0.5 crystallizes at 100 K in the Cs 7Cd3Br17 structure type in space group D4h 18-I4/mcm of the tetragonal system. The compound Ba 7UFe2S12.5O0.5 crystallizes at 100 K in space group D4h5-P4/mbm of the tetragonal system. The structures are very similar with V/S or Fe/S networks in which Ba atoms reside as well as channels large enough to accommodate additional Ba atoms and infinite linear US5O chains. Each U atom is octahedrally coordinated to four equatorial S atoms, one axial S atom, and one axial O atom. The Fe/S network contains a S-S single bond, whereas the V/S network does not. The result is that the Fe3+ compound charge balances with 7 Ba2+, U 4+, 2 Fe3+, 10.5 S2-, S2 2-, and 0.5 O2-, whereas the V4+ compound charge balances with 7 Ba2+, U4+, 2 V4+, 12.5 S2-, and 0.5 O2-. Other differences between these two compounds have been characterized by Raman spectroscopy and resistivity measurements. DFT calculations have provided insight into the nature of their bonding. The overall structural motif of Ba7UV2S 12.5O0.5 and Ba7UFe2S 12.5O0.5 offers a remarkable flexibility in terms of the oxidation state of the incorporated transition metal.
AB - Two new compounds, Ba7UV2S12.5O 0.5 and Ba7UFe2S12.5O0.5, have been synthesized in fused-silica tubes by the direct combinations of V or Fe with U, BaS, and S at 1223 K. The compound Ba7UV2S 12.5O0.5 crystallizes at 100 K in the Cs 7Cd3Br17 structure type in space group D4h 18-I4/mcm of the tetragonal system. The compound Ba 7UFe2S12.5O0.5 crystallizes at 100 K in space group D4h5-P4/mbm of the tetragonal system. The structures are very similar with V/S or Fe/S networks in which Ba atoms reside as well as channels large enough to accommodate additional Ba atoms and infinite linear US5O chains. Each U atom is octahedrally coordinated to four equatorial S atoms, one axial S atom, and one axial O atom. The Fe/S network contains a S-S single bond, whereas the V/S network does not. The result is that the Fe3+ compound charge balances with 7 Ba2+, U 4+, 2 Fe3+, 10.5 S2-, S2 2-, and 0.5 O2-, whereas the V4+ compound charge balances with 7 Ba2+, U4+, 2 V4+, 12.5 S2-, and 0.5 O2-. Other differences between these two compounds have been characterized by Raman spectroscopy and resistivity measurements. DFT calculations have provided insight into the nature of their bonding. The overall structural motif of Ba7UV2S 12.5O0.5 and Ba7UFe2S 12.5O0.5 offers a remarkable flexibility in terms of the oxidation state of the incorporated transition metal.
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U2 - 10.1021/ic401871x
DO - 10.1021/ic401871x
M3 - Article
C2 - 24107107
AN - SCOPUS:84886683941
SN - 0020-1669
VL - 52
SP - 12057
EP - 12063
JO - Inorganic chemistry
JF - Inorganic chemistry
IS - 20
ER -