Synthesis, Interconversions, and Structural Characterization of the [(S4)2MoS]2−, [(S4)2MoO]2−, (Mo2S10)2−, and (Mo2S12)2− Anions

M. Draganjac, E. Simhon, L. T. Chan, M. Kanatzidis, N. C. Baenziger, D. Coucouvanis*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

154 Scopus citations


The MoS42− anion reacts with elemental sulfur and “active” sulfur reagents such as organic trisulfides or ammonium sulfides to afford binary molybdenum sulfides. The successful isolation of these sulfides, which appear to be components of a complex equilibrium system, depends on the solvent system and the nature of the counterions present in solution. With (C2H5)4N+ as the counterion the [(S4)2MoS]2− anion, I, can be isolated from either CH3CN or DMF solutions. The hydrolysis of I in DMF or CH3CN affords the [(S4)2MoO]2− anion, II. In the presence of the (C6H5)4P+ cation the (Mo2S10)2− (III) and (Mo2S12)2− (IV) anions can be isolated from DMF solutions as mixed-anion (C6H5)4P+ salts. Both I and II crystallize in the orthorhombic space group Ibca with eight molecules in the unit cell. The cell dimensions are a = 15.594 (3) Å, b = 13.264 (4) Å, and c = 27.577 (5) Å for I and a = 15.470 (1) Å, b = 13.224 (2) Å, and c = 27.425 (3) Å for II. In the structure of III/IV, both anions occupy the same position in the crystal lattice, with III being the major component (72%). III/IV crystallizes in the triclinic space group P1̄ with two molecules per unit cell. The cell dimensions are a = 22.288 (4) Å, b = 11.724 (4) Å, c = 10.512 (2) Å, α = 78.06 (4)°, β = 86.00 (3)°, and γ = 76.10 (3)°. Intensity data for all three structures were collected with a four-circle computer-controlled diffractometer by the θ−2θ scan technique. For I and II, all non-hydrogen atoms were refined with anisotropic thermal parameters. For III/IV, the S22− ligand of Mo2S102− and the S42− ligand of Mo2S122−, as well as the DMF molecule of crystallization, were refined with isotropic thermal parameters. The remaining non-hydrogen atoms were refined with anisotropic thermal parameters. Refinement by a full-matrix least-squares procedure, of 145 parameters on 2146 data for I, 145 parameters on 1175 data for II, and 585 parameters on 7022 data for III/IV, gave final R values of 0.025, 0.047, and 0.065, respectively. In I and II, the Mo(IV) ion is coordinated by two bidentate S42− chelates and a terminal sulfur or oxygen atom in a distorted-square-pyramidal arrangement. The molybdenum is situated above the basal sulfur plane by 0.72 Å for I and 0.76 Å for II. The Mo2S102− and Mo2S122− anions have in common the (Mo2S4)2+ core as well as the tetrasulfide ligand attached to Mo(1). Mo(2) is coordinated by either a persulfido group in III or a tetrasulfido unit in compound IV. The core contains two (Mov=S)3+ units bridged asymmetrically by two sulfide ligands in the syn configuration, with a Mo—Mo distance of 2.846 (1) Å. In all three structures, an alternation of the S-S bond lengths in the S42− chelate rings is observed, and the Mo-S4 ring is in the “puckered” or envelope configuration. The coordinated sulfur atoms of the S42− ligand are asymmetrically bound to the molybdenum. The MoS4 ring conformation and the consequent effects on Mo-S bonding are attributed to intraligand sulfur electron lone-pair repulsions.

Original languageEnglish (US)
Pages (from-to)3321-3332
Number of pages12
JournalInorganic chemistry
Issue number9
StatePublished - 1982

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry


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