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• W1977865879 abstract "Ba15Fe7S25 is prepared by reacting stoichiometric amounts of BaS, Fe, and S in evacuated quartz ampoules while Ba3FeS5 is obtained in a tetrahedral press at 50 kbars and 1000°C. The crystal structure of Ba15Fe7S25 has been determined using 4053 independent, nonzero X-ray reflections measured by a counter technique. The compound crystallizes in the orthorhombic system, Pnma, a = 41.91(1) Å, b = 9.572(3) Å, c = 12.654(3) Å, ϱcalc = 4.26 g/cm3, z = 4; Ba3FeS5 also crystallizes in Pnma, a = 12.405(1) Å, b = 9.516(1) Å, c = 8.5212(9)Å, ϱcalc = 4.14 g/cm3, z = 4. In both compounds, Fe is tetrahedrally coordinated to S, and Ba is in either nine- or eight-fold coordination; a trigonal prism with three rectangular faces capped and a cube. BaS distances are about 3.4 Å, and FeS distances are 2.26 Å. In Ba3FeS5, single isolated tetrahedra are present. In Ba15Fe7S25, eight isolated trinuclear units, formed by a central tetrahedron sharing one edge and one corner, respectively, with two terminal tetrahedra and four isolated single tetrahedra are present in the unit cell. The BaS6 trigonal prisms form infinite columns by sharing the triangular faces. The columns share edges to form distorted hexagonal rings. Within the rings are additional S and Ba ions, and Fe in tetrahedral sites. The main difference between the two structures is the filling of the tetrahedral sites inside the hexagonal rings. The effective paramagnetic moment in Ba15Fe7S25 is 5.5 μB, in good agreement with a value expected from 6Fe3+ and Fe2+ from the stoichiometry. The room temperature Mössbauer spectrum shows isomer shifts of 0.2 mm/sec. The data indicate that electron delocalization occurs across the edge-shared tetrahedra so that an effective charge distribution 5Fe3+ and 2Fe2.5+ is present. The material has a room temperature electrical resistivity of 105 ohm-cm. The effective magnetic moment for Ba3FeS5 is 5.1 μB as might be expected for Fe2+ or Fe4+. One quadrupole split Mössbauer spectrum is observed with an isomer shift of 0.2 mm/sec, a value usually observed for Fe3+. The observations are reconciled by postulating the delocalization of an electron within the tetrahedral configuration. The room temperature electrical resistivity is 105 ohm-cm." @default.
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• W1977865879 date "1976-01-01" @default.
• W1977865879 modified "2023-10-14" @default.
• W1977865879 title "Ba15Fe7S25 and Ba3FeS5: Crystal structures, Mössbauer, magnetic, and electrical behavior" @default.
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• W1977865879 doi "https://doi.org/10.1016/0022-4596(76)90013-x" @default.
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