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 P1̅ (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(s7)]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 P1̅ (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 [In2S16]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
DOIs
Publication statusPublished - Jan 1 1993

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ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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