Heavy metal complexes of macrocyclic trithioethers

Monte Helm, Kristi D. Loveday, Charles M. Combs, Elizabeth L. Bentzen, Donald G. VanDerveer, Robin D. Rogers, Gregory J. Grant

Research output: Contribution to journalArticle

8 Citations (Scopus)

Abstract

We report here two crystal structures of heavy metal complexes containing macrocyclic trithioethers. The trithioether, 10S3 (1,4,7-trithiacyclodecane) complexes Pb(II) to form a compound of the formula [Pb(10S3)](ClO 4)2(H2O) (Compound 1). This behavior contrasts the related trithioether 9S3 (1,4,7-trithianonane), which readily forms a bis Pb(II) complex. Crystals of Compound 1 consist of [Pb(10S3)(H 2O)]2+ units and perchlorate anions which are weakly bound to the Pb2+ center. The two perchlorate anions serve as bidentate ligands to a single lead(II) center. However, a third oxygen in one of the perchlorates also serves as a bridging group between two lead(II) centers, linking the [Pb(10S3)(H2O)]2+ units into zigzag chains. Thus, a highly irregular nine-coordinate (S3O6) environment around the Pb2+ion is formed by the three sulfur donors from the 10S3 ligand, one coordinated water, and five oxygens from three different perchlorate anions. Also, the lone pair electrons on the Pb center are stereochemically active. Compound 2, [Cd(9S3)2](ClO 4)2 · 2 CH3NO2, forms a distorted octahedral structure with unusual hexakis(thioether) coordination to the Cd(II) center. Bond distances and angles are very comparable to those found in the structure of the tetrafluoroborate salt of the complex cation. (1): P21/c, a = 9.1720(6) Å, b = 15.7687(11) Å, c = 11.8427(8) Å, β= 93.0180(10)°, V = 1710.4 (2) Å3, Z = 4; (2): P21/c, a = 10.4305(10) Å, b = 15.2059(6) Å, c = 9.4919(7) Å, β = 99.324(9)°, V = 1485.6(2) Å3, Z = 2.

Original languageEnglish
Pages (from-to)447-455
Number of pages9
JournalJournal of Chemical Crystallography
Volume33
Issue number5-6
DOIs
Publication statusPublished - Jun 2003

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Coordination Complexes
heavy metals
Heavy Metals
Anions
perchlorates
Perchlorates
Oxygen
Ligands
anions
Sulfides
Sulfur
Cations
Salts
Crystal structure
ligands
Electrons
Ions
oxygen
Crystals
Water

Keywords

  • 1,4,7-trithiacyclononane
  • Cadmium complexes
  • Crown thioethers
  • Lead complexes
  • Stereochemically active lone pair

ASJC Scopus subject areas

  • Spectroscopy
  • Condensed Matter Physics
  • Structural Biology

Cite this

Helm, M., Loveday, K. D., Combs, C. M., Bentzen, E. L., VanDerveer, D. G., Rogers, R. D., & Grant, G. J. (2003). Heavy metal complexes of macrocyclic trithioethers. Journal of Chemical Crystallography, 33(5-6), 447-455. https://doi.org/10.1023/A:1024294417454

Heavy metal complexes of macrocyclic trithioethers. / Helm, Monte; Loveday, Kristi D.; Combs, Charles M.; Bentzen, Elizabeth L.; VanDerveer, Donald G.; Rogers, Robin D.; Grant, Gregory J.

In: Journal of Chemical Crystallography, Vol. 33, No. 5-6, 06.2003, p. 447-455.

Research output: Contribution to journalArticle

Helm, M, Loveday, KD, Combs, CM, Bentzen, EL, VanDerveer, DG, Rogers, RD & Grant, GJ 2003, 'Heavy metal complexes of macrocyclic trithioethers', Journal of Chemical Crystallography, vol. 33, no. 5-6, pp. 447-455. https://doi.org/10.1023/A:1024294417454
Helm M, Loveday KD, Combs CM, Bentzen EL, VanDerveer DG, Rogers RD et al. Heavy metal complexes of macrocyclic trithioethers. Journal of Chemical Crystallography. 2003 Jun;33(5-6):447-455. https://doi.org/10.1023/A:1024294417454
Helm, Monte ; Loveday, Kristi D. ; Combs, Charles M. ; Bentzen, Elizabeth L. ; VanDerveer, Donald G. ; Rogers, Robin D. ; Grant, Gregory J. / Heavy metal complexes of macrocyclic trithioethers. In: Journal of Chemical Crystallography. 2003 ; Vol. 33, No. 5-6. pp. 447-455.
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abstract = "We report here two crystal structures of heavy metal complexes containing macrocyclic trithioethers. The trithioether, 10S3 (1,4,7-trithiacyclodecane) complexes Pb(II) to form a compound of the formula [Pb(10S3)](ClO 4)2(H2O) (Compound 1). This behavior contrasts the related trithioether 9S3 (1,4,7-trithianonane), which readily forms a bis Pb(II) complex. Crystals of Compound 1 consist of [Pb(10S3)(H 2O)]2+ units and perchlorate anions which are weakly bound to the Pb2+ center. The two perchlorate anions serve as bidentate ligands to a single lead(II) center. However, a third oxygen in one of the perchlorates also serves as a bridging group between two lead(II) centers, linking the [Pb(10S3)(H2O)]2+ units into zigzag chains. Thus, a highly irregular nine-coordinate (S3O6) environment around the Pb2+ion is formed by the three sulfur donors from the 10S3 ligand, one coordinated water, and five oxygens from three different perchlorate anions. Also, the lone pair electrons on the Pb center are stereochemically active. Compound 2, [Cd(9S3)2](ClO 4)2 · 2 CH3NO2, forms a distorted octahedral structure with unusual hexakis(thioether) coordination to the Cd(II) center. Bond distances and angles are very comparable to those found in the structure of the tetrafluoroborate salt of the complex cation. (1): P21/c, a = 9.1720(6) {\AA}, b = 15.7687(11) {\AA}, c = 11.8427(8) {\AA}, β= 93.0180(10)°, V = 1710.4 (2) {\AA}3, Z = 4; (2): P21/c, a = 10.4305(10) {\AA}, b = 15.2059(6) {\AA}, c = 9.4919(7) {\AA}, β = 99.324(9)°, V = 1485.6(2) {\AA}3, Z = 2.",
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T1 - Heavy metal complexes of macrocyclic trithioethers

AU - Helm, Monte

AU - Loveday, Kristi D.

AU - Combs, Charles M.

AU - Bentzen, Elizabeth L.

AU - VanDerveer, Donald G.

AU - Rogers, Robin D.

AU - Grant, Gregory J.

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N2 - We report here two crystal structures of heavy metal complexes containing macrocyclic trithioethers. The trithioether, 10S3 (1,4,7-trithiacyclodecane) complexes Pb(II) to form a compound of the formula [Pb(10S3)](ClO 4)2(H2O) (Compound 1). This behavior contrasts the related trithioether 9S3 (1,4,7-trithianonane), which readily forms a bis Pb(II) complex. Crystals of Compound 1 consist of [Pb(10S3)(H 2O)]2+ units and perchlorate anions which are weakly bound to the Pb2+ center. The two perchlorate anions serve as bidentate ligands to a single lead(II) center. However, a third oxygen in one of the perchlorates also serves as a bridging group between two lead(II) centers, linking the [Pb(10S3)(H2O)]2+ units into zigzag chains. Thus, a highly irregular nine-coordinate (S3O6) environment around the Pb2+ion is formed by the three sulfur donors from the 10S3 ligand, one coordinated water, and five oxygens from three different perchlorate anions. Also, the lone pair electrons on the Pb center are stereochemically active. Compound 2, [Cd(9S3)2](ClO 4)2 · 2 CH3NO2, forms a distorted octahedral structure with unusual hexakis(thioether) coordination to the Cd(II) center. Bond distances and angles are very comparable to those found in the structure of the tetrafluoroborate salt of the complex cation. (1): P21/c, a = 9.1720(6) Å, b = 15.7687(11) Å, c = 11.8427(8) Å, β= 93.0180(10)°, V = 1710.4 (2) Å3, Z = 4; (2): P21/c, a = 10.4305(10) Å, b = 15.2059(6) Å, c = 9.4919(7) Å, β = 99.324(9)°, V = 1485.6(2) Å3, Z = 2.

AB - We report here two crystal structures of heavy metal complexes containing macrocyclic trithioethers. The trithioether, 10S3 (1,4,7-trithiacyclodecane) complexes Pb(II) to form a compound of the formula [Pb(10S3)](ClO 4)2(H2O) (Compound 1). This behavior contrasts the related trithioether 9S3 (1,4,7-trithianonane), which readily forms a bis Pb(II) complex. Crystals of Compound 1 consist of [Pb(10S3)(H 2O)]2+ units and perchlorate anions which are weakly bound to the Pb2+ center. The two perchlorate anions serve as bidentate ligands to a single lead(II) center. However, a third oxygen in one of the perchlorates also serves as a bridging group between two lead(II) centers, linking the [Pb(10S3)(H2O)]2+ units into zigzag chains. Thus, a highly irregular nine-coordinate (S3O6) environment around the Pb2+ion is formed by the three sulfur donors from the 10S3 ligand, one coordinated water, and five oxygens from three different perchlorate anions. Also, the lone pair electrons on the Pb center are stereochemically active. Compound 2, [Cd(9S3)2](ClO 4)2 · 2 CH3NO2, forms a distorted octahedral structure with unusual hexakis(thioether) coordination to the Cd(II) center. Bond distances and angles are very comparable to those found in the structure of the tetrafluoroborate salt of the complex cation. (1): P21/c, a = 9.1720(6) Å, b = 15.7687(11) Å, c = 11.8427(8) Å, β= 93.0180(10)°, V = 1710.4 (2) Å3, Z = 4; (2): P21/c, a = 10.4305(10) Å, b = 15.2059(6) Å, c = 9.4919(7) Å, β = 99.324(9)°, V = 1485.6(2) Å3, Z = 2.

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KW - Crown thioethers

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KW - Stereochemically active lone pair

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