The crystal and molecular structure of bis(ethyl thioxanthato)-μ-bis(ethyl thioxanthato)-μ′-bis(ethylthio)-diiron(III)

D. Coucouvanis, S. J. Lippard, Jon A Zubieta

Research output: Contribution to journalArticle

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Abstract

The molecular structure of bis(ethyl thioxanthato)-μ-bis(ethyl thioxanthato)-μ′-bis(ethylthio)-diiron(III), [Fe(SC2H5)(S2CSC2H5) 2]2, has been determined in a single-crystal X-ray diffraction study. The complex crystallizes in the monoclinic system, space group P21/c, with a = 12.193 (5) Å, b = 8.469 (4) Å, c = 19.82 (1) Å, and β = 130.11 (5)°. The density of 1.657 (1) g/cm3 calculated on the basis of two dimeric formulas per unit cell is in agreement with the measured density of 1.64 ± 0.01 g/cm3. The structure was solved using ∼1350 independent, statistically significant reflections collected on a full-circle automated diffractometer. Refinement of all atoms including several of the hydrogen atoms led to a final value of the discrepancy index, R1, of 0.048. The molecular structure consists of centrosymmetric dimers in which two ethyl mercaptide and two ethylthioxanthate groups function as bridging ligands and two more nonbridging ethylthioxanthate ligands complete the distorted octahedral coordination polyhedra around the two iron atoms. The iron-iron distance of 2.618 (2) Å is 0.39 Å shorter than the S⋯S bite of the bridging thioxanthate ligand. This result, together with the small Fe-S-Fe angle of 72.35 (7)° at the bridging sulfur atoms, provides direct structural proof for metal-metal bonding. Average values for the three chemically distinct types of iron-sulfur bonds in the molecule are 2.218 (2) Å for the bridging mercaptide ligands, 2.287 (2) Å for the bridging thioxanthate ligands, and 2.338 (4) Å for the terminal thioxanthate ligands. From the observed carbon-sulfur distances it is concluded that resonance form VII (see text) contributes significantly (∼20%) to the electronic structure of the coordinated thioxanthate groups.

Original languageEnglish (US)
Pages (from-to)2775-2781
Number of pages7
JournalInorganic Chemistry
Volume9
Issue number12
StatePublished - 1970
Externally publishedYes

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Molecular structure
molecular structure
Crystal structure
Ligands
ligands
crystal structure
Iron
Sulfur
iron
Atoms
sulfur
Metals
metal-metal bonding
atoms
Diffractometers
polyhedrons
diffractometers
Dimers
Electronic structure
Hydrogen

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

The crystal and molecular structure of bis(ethyl thioxanthato)-μ-bis(ethyl thioxanthato)-μ′-bis(ethylthio)-diiron(III). / Coucouvanis, D.; Lippard, S. J.; Zubieta, Jon A.

In: Inorganic Chemistry, Vol. 9, No. 12, 1970, p. 2775-2781.

Research output: Contribution to journalArticle

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title = "The crystal and molecular structure of bis(ethyl thioxanthato)-μ-bis(ethyl thioxanthato)-μ′-bis(ethylthio)-diiron(III)",
abstract = "The molecular structure of bis(ethyl thioxanthato)-μ-bis(ethyl thioxanthato)-μ′-bis(ethylthio)-diiron(III), [Fe(SC2H5)(S2CSC2H5) 2]2, has been determined in a single-crystal X-ray diffraction study. The complex crystallizes in the monoclinic system, space group P21/c, with a = 12.193 (5) {\AA}, b = 8.469 (4) {\AA}, c = 19.82 (1) {\AA}, and β = 130.11 (5)°. The density of 1.657 (1) g/cm3 calculated on the basis of two dimeric formulas per unit cell is in agreement with the measured density of 1.64 ± 0.01 g/cm3. The structure was solved using ∼1350 independent, statistically significant reflections collected on a full-circle automated diffractometer. Refinement of all atoms including several of the hydrogen atoms led to a final value of the discrepancy index, R1, of 0.048. The molecular structure consists of centrosymmetric dimers in which two ethyl mercaptide and two ethylthioxanthate groups function as bridging ligands and two more nonbridging ethylthioxanthate ligands complete the distorted octahedral coordination polyhedra around the two iron atoms. The iron-iron distance of 2.618 (2) {\AA} is 0.39 {\AA} shorter than the S⋯S bite of the bridging thioxanthate ligand. This result, together with the small Fe-S-Fe angle of 72.35 (7)° at the bridging sulfur atoms, provides direct structural proof for metal-metal bonding. Average values for the three chemically distinct types of iron-sulfur bonds in the molecule are 2.218 (2) {\AA} for the bridging mercaptide ligands, 2.287 (2) {\AA} for the bridging thioxanthate ligands, and 2.338 (4) {\AA} for the terminal thioxanthate ligands. From the observed carbon-sulfur distances it is concluded that resonance form VII (see text) contributes significantly (∼20{\%}) to the electronic structure of the coordinated thioxanthate groups.",
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T1 - The crystal and molecular structure of bis(ethyl thioxanthato)-μ-bis(ethyl thioxanthato)-μ′-bis(ethylthio)-diiron(III)

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N2 - The molecular structure of bis(ethyl thioxanthato)-μ-bis(ethyl thioxanthato)-μ′-bis(ethylthio)-diiron(III), [Fe(SC2H5)(S2CSC2H5) 2]2, has been determined in a single-crystal X-ray diffraction study. The complex crystallizes in the monoclinic system, space group P21/c, with a = 12.193 (5) Å, b = 8.469 (4) Å, c = 19.82 (1) Å, and β = 130.11 (5)°. The density of 1.657 (1) g/cm3 calculated on the basis of two dimeric formulas per unit cell is in agreement with the measured density of 1.64 ± 0.01 g/cm3. The structure was solved using ∼1350 independent, statistically significant reflections collected on a full-circle automated diffractometer. Refinement of all atoms including several of the hydrogen atoms led to a final value of the discrepancy index, R1, of 0.048. The molecular structure consists of centrosymmetric dimers in which two ethyl mercaptide and two ethylthioxanthate groups function as bridging ligands and two more nonbridging ethylthioxanthate ligands complete the distorted octahedral coordination polyhedra around the two iron atoms. The iron-iron distance of 2.618 (2) Å is 0.39 Å shorter than the S⋯S bite of the bridging thioxanthate ligand. This result, together with the small Fe-S-Fe angle of 72.35 (7)° at the bridging sulfur atoms, provides direct structural proof for metal-metal bonding. Average values for the three chemically distinct types of iron-sulfur bonds in the molecule are 2.218 (2) Å for the bridging mercaptide ligands, 2.287 (2) Å for the bridging thioxanthate ligands, and 2.338 (4) Å for the terminal thioxanthate ligands. From the observed carbon-sulfur distances it is concluded that resonance form VII (see text) contributes significantly (∼20%) to the electronic structure of the coordinated thioxanthate groups.

AB - The molecular structure of bis(ethyl thioxanthato)-μ-bis(ethyl thioxanthato)-μ′-bis(ethylthio)-diiron(III), [Fe(SC2H5)(S2CSC2H5) 2]2, has been determined in a single-crystal X-ray diffraction study. The complex crystallizes in the monoclinic system, space group P21/c, with a = 12.193 (5) Å, b = 8.469 (4) Å, c = 19.82 (1) Å, and β = 130.11 (5)°. The density of 1.657 (1) g/cm3 calculated on the basis of two dimeric formulas per unit cell is in agreement with the measured density of 1.64 ± 0.01 g/cm3. The structure was solved using ∼1350 independent, statistically significant reflections collected on a full-circle automated diffractometer. Refinement of all atoms including several of the hydrogen atoms led to a final value of the discrepancy index, R1, of 0.048. The molecular structure consists of centrosymmetric dimers in which two ethyl mercaptide and two ethylthioxanthate groups function as bridging ligands and two more nonbridging ethylthioxanthate ligands complete the distorted octahedral coordination polyhedra around the two iron atoms. The iron-iron distance of 2.618 (2) Å is 0.39 Å shorter than the S⋯S bite of the bridging thioxanthate ligand. This result, together with the small Fe-S-Fe angle of 72.35 (7)° at the bridging sulfur atoms, provides direct structural proof for metal-metal bonding. Average values for the three chemically distinct types of iron-sulfur bonds in the molecule are 2.218 (2) Å for the bridging mercaptide ligands, 2.287 (2) Å for the bridging thioxanthate ligands, and 2.338 (4) Å for the terminal thioxanthate ligands. From the observed carbon-sulfur distances it is concluded that resonance form VII (see text) contributes significantly (∼20%) to the electronic structure of the coordinated thioxanthate groups.

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