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 language | English |
|---|---|
| Pages (from-to) | 447-455 |
| Number of pages | 9 |
| Journal | Journal of Chemical Crystallography |
| Volume | 33 |
| Issue number | 5-6 |
| DOIs | |
| Publication status | Published - Jun 2003 |
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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
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 journal › Article
}
TY - JOUR
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.
PY - 2003/6
Y1 - 2003/6
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.
KW - 1,4,7-trithiacyclononane
KW - Cadmium complexes
KW - Crown thioethers
KW - Lead complexes
KW - Stereochemically active lone pair
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UR - http://www.scopus.com/inward/citedby.url?scp=0037786723&partnerID=8YFLogxK
U2 - 10.1023/A:1024294417454
DO - 10.1023/A:1024294417454
M3 - Article
VL - 33
SP - 447
EP - 455
JO - Journal of Crystallographic and Spectroscopic Research
JF - Journal of Crystallographic and Spectroscopic Research
SN - 0277-8068
IS - 5-6
ER -