Syntheses and characterization of the new homoleptic indium-polysulfide complexes [In2S27]4-, [In2S14]2-, and [In2S16]2-

Sandeep S. Dhingra, Mercouri G Kanatzidis

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Abstract

The reaction of InCl3 with K2S5 and Ph4PCl in a 2:5:4 mole ratio in DMF afforded thin pale yellow crystals of (Ph4P)4[In2S27] (I). I crystallizes in the triclinic space group P1 (No. 2) with a = 12.276(3) Å, b = 21.849(8) Å, c = 10.852(2) Å, α = 99.57(2)°, β = 112.44(2)°, γ = 79.28(3)°, V = 2628(1) Å3 (at -90°C), and Z = 1. The [In2(S4)2(S6)2(S 7)]4- anion consists of In3+ centers in trigonal bipyramidal coordination. Each In atom is chelated by two bidentate polysulfide S42- and S62- ligands forming a [In(S4)(S6)]- unit. Two [In(S4)(S6)]- units are bridged by an S72- chain forming a dimer. A similar reaction of InCl3 with K2S5 and Ph4PCl in a slightly different mole ratio of 1:2:1 in DMF afforded pale yellow crystals of (Ph4P)2{[In2S14] 0.5[In2S16]0.5} (II). II crystallizes in the triclinic space group P1 (No. 2) with a = 10.906(2) Å, b = 11.892(2) Å, c = 21.554(3) Å, α = 89.81(1)°, β = 97.46(1)°, γ = 92.25(1)°, V = 2769(1) Å3 (at -80°C), and Z = 2. II is a cocrystallizate of [In2S14]2- and [In2Si6]2- anions with equal occupancies. The two anions contain tetrahedral In3+ centers. The In atoms are bridged by an S2- and an S52- ligand to form an eight-membered [In2S(S5)]2+ ring core in an extreme cradle configuration. The remaining two coordination sites on each In atom are occupied by a S42- chelating ligand on one side and a S42- or a S62- chelating ligand disordered on the other. These complexes show no absorption peaks in the UV/vis region of the spectrum. The solid-state far-IR spectra of the compounds exhibit strong absorptions in the 500-100-cm-1 region due to the S-S and M-S stretching vibrations. Thermal gravimetric analysis data for these compounds are reported.

Original languageEnglish
Pages (from-to)3300-3305
Number of pages6
JournalInorganic Chemistry
Volume32
Issue number15
Publication statusPublished - 1993

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polysulfides
Indium
indium
Ligands
Anions
ligands
synthesis
Chelation
anions
Atoms
atoms
Crystals
Gravimetric analysis
Dimers
Stretching
crystals
thermal analysis
dimers
solid state
vibration

ASJC Scopus subject areas

  • Inorganic Chemistry

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Syntheses and characterization of the new homoleptic indium-polysulfide complexes [In2S27]4-, [In2S14]2-, and [In2S16]2-. / Dhingra, Sandeep S.; Kanatzidis, Mercouri G.

In: Inorganic Chemistry, Vol. 32, No. 15, 1993, p. 3300-3305.

Research output: Contribution to journalArticle

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title = "Syntheses and characterization of the new homoleptic indium-polysulfide complexes [In2S27]4-, [In2S14]2-, and [In2S16]2-",
abstract = "The reaction of InCl3 with K2S5 and Ph4PCl in a 2:5:4 mole ratio in DMF afforded thin pale yellow crystals of (Ph4P)4[In2S27] (I). I crystallizes in the triclinic space group P1 (No. 2) with a = 12.276(3) {\AA}, b = 21.849(8) {\AA}, c = 10.852(2) {\AA}, α = 99.57(2)°, β = 112.44(2)°, γ = 79.28(3)°, V = 2628(1) {\AA}3 (at -90°C), and Z = 1. The [In2(S4)2(S6)2(S 7)]4- anion consists of In3+ centers in trigonal bipyramidal coordination. Each In atom is chelated by two bidentate polysulfide S42- and S62- ligands forming a [In(S4)(S6)]- unit. Two [In(S4)(S6)]- units are bridged by an S72- chain forming a dimer. A similar reaction of InCl3 with K2S5 and Ph4PCl in a slightly different mole ratio of 1:2:1 in DMF afforded pale yellow crystals of (Ph4P)2{[In2S14] 0.5[In2S16]0.5} (II). II crystallizes in the triclinic space group P1 (No. 2) with a = 10.906(2) {\AA}, b = 11.892(2) {\AA}, c = 21.554(3) {\AA}, α = 89.81(1)°, β = 97.46(1)°, γ = 92.25(1)°, V = 2769(1) {\AA}3 (at -80°C), and Z = 2. II is a cocrystallizate of [In2S14]2- and [In2Si6]2- anions with equal occupancies. The two anions contain tetrahedral In3+ centers. The In atoms are bridged by an S2- and an S52- ligand to form an eight-membered [In2S(S5)]2+ ring core in an extreme cradle configuration. The remaining two coordination sites on each In atom are occupied by a S42- chelating ligand on one side and a S42- or a S62- chelating ligand disordered on the other. These complexes show no absorption peaks in the UV/vis region of the spectrum. The solid-state far-IR spectra of the compounds exhibit strong absorptions in the 500-100-cm-1 region due to the S-S and M-S stretching vibrations. Thermal gravimetric analysis data for these compounds are reported.",
author = "Dhingra, {Sandeep S.} and Kanatzidis, {Mercouri G}",
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T1 - Syntheses and characterization of the new homoleptic indium-polysulfide complexes [In2S27]4-, [In2S14]2-, and [In2S16]2-

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AU - Kanatzidis, Mercouri G

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N2 - The reaction of InCl3 with K2S5 and Ph4PCl in a 2:5:4 mole ratio in DMF afforded thin pale yellow crystals of (Ph4P)4[In2S27] (I). I crystallizes in the triclinic space group P1 (No. 2) with a = 12.276(3) Å, b = 21.849(8) Å, c = 10.852(2) Å, α = 99.57(2)°, β = 112.44(2)°, γ = 79.28(3)°, V = 2628(1) Å3 (at -90°C), and Z = 1. The [In2(S4)2(S6)2(S 7)]4- anion consists of In3+ centers in trigonal bipyramidal coordination. Each In atom is chelated by two bidentate polysulfide S42- and S62- ligands forming a [In(S4)(S6)]- unit. Two [In(S4)(S6)]- units are bridged by an S72- chain forming a dimer. A similar reaction of InCl3 with K2S5 and Ph4PCl in a slightly different mole ratio of 1:2:1 in DMF afforded pale yellow crystals of (Ph4P)2{[In2S14] 0.5[In2S16]0.5} (II). II crystallizes in the triclinic space group P1 (No. 2) with a = 10.906(2) Å, b = 11.892(2) Å, c = 21.554(3) Å, α = 89.81(1)°, β = 97.46(1)°, γ = 92.25(1)°, V = 2769(1) Å3 (at -80°C), and Z = 2. II is a cocrystallizate of [In2S14]2- and [In2Si6]2- anions with equal occupancies. The two anions contain tetrahedral In3+ centers. The In atoms are bridged by an S2- and an S52- ligand to form an eight-membered [In2S(S5)]2+ ring core in an extreme cradle configuration. The remaining two coordination sites on each In atom are occupied by a S42- chelating ligand on one side and a S42- or a S62- chelating ligand disordered on the other. These complexes show no absorption peaks in the UV/vis region of the spectrum. The solid-state far-IR spectra of the compounds exhibit strong absorptions in the 500-100-cm-1 region due to the S-S and M-S stretching vibrations. Thermal gravimetric analysis data for these compounds are reported.

AB - The reaction of InCl3 with K2S5 and Ph4PCl in a 2:5:4 mole ratio in DMF afforded thin pale yellow crystals of (Ph4P)4[In2S27] (I). I crystallizes in the triclinic space group P1 (No. 2) with a = 12.276(3) Å, b = 21.849(8) Å, c = 10.852(2) Å, α = 99.57(2)°, β = 112.44(2)°, γ = 79.28(3)°, V = 2628(1) Å3 (at -90°C), and Z = 1. The [In2(S4)2(S6)2(S 7)]4- anion consists of In3+ centers in trigonal bipyramidal coordination. Each In atom is chelated by two bidentate polysulfide S42- and S62- ligands forming a [In(S4)(S6)]- unit. Two [In(S4)(S6)]- units are bridged by an S72- chain forming a dimer. A similar reaction of InCl3 with K2S5 and Ph4PCl in a slightly different mole ratio of 1:2:1 in DMF afforded pale yellow crystals of (Ph4P)2{[In2S14] 0.5[In2S16]0.5} (II). II crystallizes in the triclinic space group P1 (No. 2) with a = 10.906(2) Å, b = 11.892(2) Å, c = 21.554(3) Å, α = 89.81(1)°, β = 97.46(1)°, γ = 92.25(1)°, V = 2769(1) Å3 (at -80°C), and Z = 2. II is a cocrystallizate of [In2S14]2- and [In2Si6]2- anions with equal occupancies. The two anions contain tetrahedral In3+ centers. The In atoms are bridged by an S2- and an S52- ligand to form an eight-membered [In2S(S5)]2+ ring core in an extreme cradle configuration. The remaining two coordination sites on each In atom are occupied by a S42- chelating ligand on one side and a S42- or a S62- chelating ligand disordered on the other. These complexes show no absorption peaks in the UV/vis region of the spectrum. The solid-state far-IR spectra of the compounds exhibit strong absorptions in the 500-100-cm-1 region due to the S-S and M-S stretching vibrations. Thermal gravimetric analysis data for these compounds are reported.

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