Polysulfide ligands in solid-state antimony compounds. Isolation and structural characterization of Cs2Sb4S8 and CsSbS6

Timothy J. McCarthy, Mercouri G Kanatzidis

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Abstract

Cs2Sb4S8 and CsSbS6 were synthesized by reacting Sb with a Cs2Sx flux. An investigation of the Sb/Cs2Sx system at 260 and 280°C revealed the presence of two new ternary sulfides, Cs2Sb4S8 (I) (67% yield) and CsSbS6 (II) (69% yield), respectively. Red-orange Cs2Sb4S8 crystallizes in the triclinic P1 space group (No. 2) with a = 6.743(1) Å, b = 9.577(2) Å, c = 6.397(1) Å, α = 91.63(1)°, β = 104.83(1)°, γ = 80.57(1)°, V = 392 Å3, Z = 1, and dcalc = 4.27g/cm3; number of data with Fo2 > 3σ(Fo2) 1889, number of variables 65, 2θmax = 60°. The final R/Rw = 3.2/4.9. The structure of I consists of [Sb4S6] units that are assembled into chains in the a direction. The chains are connected by S22- bridging units to form layers that are parallel to the (011) crystallographic plane. The layers are connected by Sb-S interactions to form channels that are filled with 10-coordinate Cs+ ions (Cs-S mean = 3.62(4) Å). Compound II crystallizes in the P21/n space group (No. 14) with a = 5.885(2) Å, b = 14.413(2) Å, c = 11.079(2) Å, β = 101.69(2)°, V = 920 Å3, Z = 4, and dcalc = 3.23g/cm3; number of data with Fo2 > 3σ(Fo2) 1926, number of variables 74, 2θmax = 60°. The final R/Rw = 2.5/3.9. The structure consists of four-membered Sb2S2 rings linked along the a axis via pentasulfide ligands to form one-dimensional chains that are separated by Cs+ ions. The band gaps of the semiconducting I and II are 2.05 and 2.25 eV, respectively. Thermal analysis data for I and II are reported.

Original languageEnglish
Pages (from-to)1205-1211
Number of pages7
JournalInorganic Chemistry
Volume33
Issue number6
Publication statusPublished - 1994

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Antimony compounds
antimony compounds
polysulfides
isolation
Ions
Ligands
solid state
ligands
Sulfides
Thermoanalysis
Energy gap
Fluxes
sulfides
thermal analysis
ions
rings
polysulfide
interactions

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

Polysulfide ligands in solid-state antimony compounds. Isolation and structural characterization of Cs2Sb4S8 and CsSbS6. / McCarthy, Timothy J.; Kanatzidis, Mercouri G.

In: Inorganic Chemistry, Vol. 33, No. 6, 1994, p. 1205-1211.

Research output: Contribution to journalArticle

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title = "Polysulfide ligands in solid-state antimony compounds. Isolation and structural characterization of Cs2Sb4S8 and CsSbS6",
abstract = "Cs2Sb4S8 and CsSbS6 were synthesized by reacting Sb with a Cs2Sx flux. An investigation of the Sb/Cs2Sx system at 260 and 280°C revealed the presence of two new ternary sulfides, Cs2Sb4S8 (I) (67{\%} yield) and CsSbS6 (II) (69{\%} yield), respectively. Red-orange Cs2Sb4S8 crystallizes in the triclinic P1 space group (No. 2) with a = 6.743(1) {\AA}, b = 9.577(2) {\AA}, c = 6.397(1) {\AA}, α = 91.63(1)°, β = 104.83(1)°, γ = 80.57(1)°, V = 392 {\AA}3, Z = 1, and dcalc = 4.27g/cm3; number of data with Fo2 > 3σ(Fo2) 1889, number of variables 65, 2θmax = 60°. The final R/Rw = 3.2/4.9. The structure of I consists of [Sb4S6] units that are assembled into chains in the a direction. The chains are connected by S22- bridging units to form layers that are parallel to the (011) crystallographic plane. The layers are connected by Sb-S interactions to form channels that are filled with 10-coordinate Cs+ ions (Cs-S mean = 3.62(4) {\AA}). Compound II crystallizes in the P21/n space group (No. 14) with a = 5.885(2) {\AA}, b = 14.413(2) {\AA}, c = 11.079(2) {\AA}, β = 101.69(2)°, V = 920 {\AA}3, Z = 4, and dcalc = 3.23g/cm3; number of data with Fo2 > 3σ(Fo2) 1926, number of variables 74, 2θmax = 60°. The final R/Rw = 2.5/3.9. The structure consists of four-membered Sb2S2 rings linked along the a axis via pentasulfide ligands to form one-dimensional chains that are separated by Cs+ ions. The band gaps of the semiconducting I and II are 2.05 and 2.25 eV, respectively. Thermal analysis data for I and II are reported.",
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N2 - Cs2Sb4S8 and CsSbS6 were synthesized by reacting Sb with a Cs2Sx flux. An investigation of the Sb/Cs2Sx system at 260 and 280°C revealed the presence of two new ternary sulfides, Cs2Sb4S8 (I) (67% yield) and CsSbS6 (II) (69% yield), respectively. Red-orange Cs2Sb4S8 crystallizes in the triclinic P1 space group (No. 2) with a = 6.743(1) Å, b = 9.577(2) Å, c = 6.397(1) Å, α = 91.63(1)°, β = 104.83(1)°, γ = 80.57(1)°, V = 392 Å3, Z = 1, and dcalc = 4.27g/cm3; number of data with Fo2 > 3σ(Fo2) 1889, number of variables 65, 2θmax = 60°. The final R/Rw = 3.2/4.9. The structure of I consists of [Sb4S6] units that are assembled into chains in the a direction. The chains are connected by S22- bridging units to form layers that are parallel to the (011) crystallographic plane. The layers are connected by Sb-S interactions to form channels that are filled with 10-coordinate Cs+ ions (Cs-S mean = 3.62(4) Å). Compound II crystallizes in the P21/n space group (No. 14) with a = 5.885(2) Å, b = 14.413(2) Å, c = 11.079(2) Å, β = 101.69(2)°, V = 920 Å3, Z = 4, and dcalc = 3.23g/cm3; number of data with Fo2 > 3σ(Fo2) 1926, number of variables 74, 2θmax = 60°. The final R/Rw = 2.5/3.9. The structure consists of four-membered Sb2S2 rings linked along the a axis via pentasulfide ligands to form one-dimensional chains that are separated by Cs+ ions. The band gaps of the semiconducting I and II are 2.05 and 2.25 eV, respectively. Thermal analysis data for I and II are reported.

AB - Cs2Sb4S8 and CsSbS6 were synthesized by reacting Sb with a Cs2Sx flux. An investigation of the Sb/Cs2Sx system at 260 and 280°C revealed the presence of two new ternary sulfides, Cs2Sb4S8 (I) (67% yield) and CsSbS6 (II) (69% yield), respectively. Red-orange Cs2Sb4S8 crystallizes in the triclinic P1 space group (No. 2) with a = 6.743(1) Å, b = 9.577(2) Å, c = 6.397(1) Å, α = 91.63(1)°, β = 104.83(1)°, γ = 80.57(1)°, V = 392 Å3, Z = 1, and dcalc = 4.27g/cm3; number of data with Fo2 > 3σ(Fo2) 1889, number of variables 65, 2θmax = 60°. The final R/Rw = 3.2/4.9. The structure of I consists of [Sb4S6] units that are assembled into chains in the a direction. The chains are connected by S22- bridging units to form layers that are parallel to the (011) crystallographic plane. The layers are connected by Sb-S interactions to form channels that are filled with 10-coordinate Cs+ ions (Cs-S mean = 3.62(4) Å). Compound II crystallizes in the P21/n space group (No. 14) with a = 5.885(2) Å, b = 14.413(2) Å, c = 11.079(2) Å, β = 101.69(2)°, V = 920 Å3, Z = 4, and dcalc = 3.23g/cm3; number of data with Fo2 > 3σ(Fo2) 1926, number of variables 74, 2θmax = 60°. The final R/Rw = 2.5/3.9. The structure consists of four-membered Sb2S2 rings linked along the a axis via pentasulfide ligands to form one-dimensional chains that are separated by Cs+ ions. The band gaps of the semiconducting I and II are 2.05 and 2.25 eV, respectively. Thermal analysis data for I and II are reported.

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