Sulfosalts with alkaline earth metals. Centrosymmetric vs acentric interplay in Ba3Sb4.66S10 and Ba2.62Pb1.38Sb4S10 based on the Ba/Pb/Sb ratio. Phases related to arsenosulfide minerals of the rathite group and the novel polysulfide Sr6Sb6S17

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Abstract

The new compounds, Sr6Sb6Sl7, Ba2.62Pb1.38Sb4S10, and Ba3Sb4.66S10 were prepared by the molten polychalcogenide salt method. Sr6Sb6S17 crystallizes in the orthorhombic space group P212121 with a = 8.2871(9) Å, b = 15.352(2) Å, c = 22.873(3) Å, and Z = 4. This compound presents a new structure type composed of [Sb3S7]5- units and trisulfide groups, (S3)2-, held together by Sr2+ ions. The [Sb3S7]5- fragment is formed from three corner-sharing SbS3 trigonal pyramids. The trisulfide groups are separated from the [Sb3S7]5- unit and embedded between the Sr2+ ions. Ba3Sb4.66S10 and Ba2.62Pb1.38Sb4S10 are not isostructural but are closely related to the known mineral sulfosalts of the rathite group. Ba3Sb4.67S10 is monoclinic P21/c with a = 8.955(2) Å, b = 8.225(2) Å, c = 26.756(5) Å, β = 100.29(3)°, and Z = 4. Ba2.62Pb1.38Sb4S10 is monoclinic P21 with a = 8.8402(2) Å, b = 8.2038(2) Å, c = 26.7623(6) Å, β = 99.488(1)°, and Z = 4. The Sb atoms are stabilized in SbS3 trigonal pyramids that share corners to build ribbonlike slabs, which are stitched by Ba/Pb atoms to form layers perpendicular to the c-axis. These materials are semiconductors and show optical band gaps of 2.10, 2.14, and 1.64 eV for Sr6Sb6Sl7, Ba3Sb4.66S10, and Ba2.62Pb1.38Sb4S10, respectively. Raman spectroscopic characterization is reported. Sr6Sb6Sl7, Ba3Sb4.66S10, and Ba2.62Pb1.38Sb4S10 melt congruently at 729, 770, and 749°C, respectively.

Original languageEnglish
Pages (from-to)5655-5662
Number of pages8
JournalInorganic Chemistry
Volume39
Issue number25
DOIs
Publication statusPublished - Dec 11 2000

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Alkaline Earth Metals
polysulfides
alkaline earth metals
Minerals
minerals
Ions
Sulfide minerals
Atoms
Optical band gaps
pyramids
Molten materials
Salts
Semiconductor materials
molten salts
atoms
ions
slabs
fragments
polysulfide

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

@article{d0440eae635e4552ad8dcf8c4dc7f3ea,
title = "Sulfosalts with alkaline earth metals. Centrosymmetric vs acentric interplay in Ba3Sb4.66S10 and Ba2.62Pb1.38Sb4S10 based on the Ba/Pb/Sb ratio. Phases related to arsenosulfide minerals of the rathite group and the novel polysulfide Sr6Sb6S17",
abstract = "The new compounds, Sr6Sb6Sl7, Ba2.62Pb1.38Sb4S10, and Ba3Sb4.66S10 were prepared by the molten polychalcogenide salt method. Sr6Sb6S17 crystallizes in the orthorhombic space group P212121 with a = 8.2871(9) {\AA}, b = 15.352(2) {\AA}, c = 22.873(3) {\AA}, and Z = 4. This compound presents a new structure type composed of [Sb3S7]5- units and trisulfide groups, (S3)2-, held together by Sr2+ ions. The [Sb3S7]5- fragment is formed from three corner-sharing SbS3 trigonal pyramids. The trisulfide groups are separated from the [Sb3S7]5- unit and embedded between the Sr2+ ions. Ba3Sb4.66S10 and Ba2.62Pb1.38Sb4S10 are not isostructural but are closely related to the known mineral sulfosalts of the rathite group. Ba3Sb4.67S10 is monoclinic P21/c with a = 8.955(2) {\AA}, b = 8.225(2) {\AA}, c = 26.756(5) {\AA}, β = 100.29(3)°, and Z = 4. Ba2.62Pb1.38Sb4S10 is monoclinic P21 with a = 8.8402(2) {\AA}, b = 8.2038(2) {\AA}, c = 26.7623(6) {\AA}, β = 99.488(1)°, and Z = 4. The Sb atoms are stabilized in SbS3 trigonal pyramids that share corners to build ribbonlike slabs, which are stitched by Ba/Pb atoms to form layers perpendicular to the c-axis. These materials are semiconductors and show optical band gaps of 2.10, 2.14, and 1.64 eV for Sr6Sb6Sl7, Ba3Sb4.66S10, and Ba2.62Pb1.38Sb4S10, respectively. Raman spectroscopic characterization is reported. Sr6Sb6Sl7, Ba3Sb4.66S10, and Ba2.62Pb1.38Sb4S10 melt congruently at 729, 770, and 749°C, respectively.",
author = "Choi, {K. S.} and Kanatzidis, {Mercouri G}",
year = "2000",
month = "12",
day = "11",
doi = "10.1021/ic000632m",
language = "English",
volume = "39",
pages = "5655--5662",
journal = "Inorganic Chemistry",
issn = "0020-1669",
publisher = "American Chemical Society",
number = "25",

}

TY - JOUR

T1 - Sulfosalts with alkaline earth metals. Centrosymmetric vs acentric interplay in Ba3Sb4.66S10 and Ba2.62Pb1.38Sb4S10 based on the Ba/Pb/Sb ratio. Phases related to arsenosulfide minerals of the rathite group and the novel polysulfide Sr6Sb6S17

AU - Choi, K. S.

AU - Kanatzidis, Mercouri G

PY - 2000/12/11

Y1 - 2000/12/11

N2 - The new compounds, Sr6Sb6Sl7, Ba2.62Pb1.38Sb4S10, and Ba3Sb4.66S10 were prepared by the molten polychalcogenide salt method. Sr6Sb6S17 crystallizes in the orthorhombic space group P212121 with a = 8.2871(9) Å, b = 15.352(2) Å, c = 22.873(3) Å, and Z = 4. This compound presents a new structure type composed of [Sb3S7]5- units and trisulfide groups, (S3)2-, held together by Sr2+ ions. The [Sb3S7]5- fragment is formed from three corner-sharing SbS3 trigonal pyramids. The trisulfide groups are separated from the [Sb3S7]5- unit and embedded between the Sr2+ ions. Ba3Sb4.66S10 and Ba2.62Pb1.38Sb4S10 are not isostructural but are closely related to the known mineral sulfosalts of the rathite group. Ba3Sb4.67S10 is monoclinic P21/c with a = 8.955(2) Å, b = 8.225(2) Å, c = 26.756(5) Å, β = 100.29(3)°, and Z = 4. Ba2.62Pb1.38Sb4S10 is monoclinic P21 with a = 8.8402(2) Å, b = 8.2038(2) Å, c = 26.7623(6) Å, β = 99.488(1)°, and Z = 4. The Sb atoms are stabilized in SbS3 trigonal pyramids that share corners to build ribbonlike slabs, which are stitched by Ba/Pb atoms to form layers perpendicular to the c-axis. These materials are semiconductors and show optical band gaps of 2.10, 2.14, and 1.64 eV for Sr6Sb6Sl7, Ba3Sb4.66S10, and Ba2.62Pb1.38Sb4S10, respectively. Raman spectroscopic characterization is reported. Sr6Sb6Sl7, Ba3Sb4.66S10, and Ba2.62Pb1.38Sb4S10 melt congruently at 729, 770, and 749°C, respectively.

AB - The new compounds, Sr6Sb6Sl7, Ba2.62Pb1.38Sb4S10, and Ba3Sb4.66S10 were prepared by the molten polychalcogenide salt method. Sr6Sb6S17 crystallizes in the orthorhombic space group P212121 with a = 8.2871(9) Å, b = 15.352(2) Å, c = 22.873(3) Å, and Z = 4. This compound presents a new structure type composed of [Sb3S7]5- units and trisulfide groups, (S3)2-, held together by Sr2+ ions. The [Sb3S7]5- fragment is formed from three corner-sharing SbS3 trigonal pyramids. The trisulfide groups are separated from the [Sb3S7]5- unit and embedded between the Sr2+ ions. Ba3Sb4.66S10 and Ba2.62Pb1.38Sb4S10 are not isostructural but are closely related to the known mineral sulfosalts of the rathite group. Ba3Sb4.67S10 is monoclinic P21/c with a = 8.955(2) Å, b = 8.225(2) Å, c = 26.756(5) Å, β = 100.29(3)°, and Z = 4. Ba2.62Pb1.38Sb4S10 is monoclinic P21 with a = 8.8402(2) Å, b = 8.2038(2) Å, c = 26.7623(6) Å, β = 99.488(1)°, and Z = 4. The Sb atoms are stabilized in SbS3 trigonal pyramids that share corners to build ribbonlike slabs, which are stitched by Ba/Pb atoms to form layers perpendicular to the c-axis. These materials are semiconductors and show optical band gaps of 2.10, 2.14, and 1.64 eV for Sr6Sb6Sl7, Ba3Sb4.66S10, and Ba2.62Pb1.38Sb4S10, respectively. Raman spectroscopic characterization is reported. Sr6Sb6Sl7, Ba3Sb4.66S10, and Ba2.62Pb1.38Sb4S10 melt congruently at 729, 770, and 749°C, respectively.

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U2 - 10.1021/ic000632m

DO - 10.1021/ic000632m

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C2 - 11151365

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