TY - JOUR
T1 - Mercury complexes with thiacrowns
T2 - The crystal structure of bis(1,4,7-trithiacyclodecane)mercury(II) hexafluorophosphate
AU - Helm, Monte L.
AU - Vanderveer, Donald G.
AU - Grant, Gregory J.
PY - 2003/8/1
Y1 - 2003/8/1
N2 - We report the synthesis, crystal structure, and NMR spectroscopy for the mercury(II) complex with the crown thioether 1,4,7-trithiacyclodecane (10S3), bis(1,4,7-trithiacyclodecane)mercury(II) hexafluorophosphate (1). The 10S3 ligand coordinates in tridentate fashion and readily forms a distorted bis octahedral complex, an unusual coordination geometry for Hg(II). The crystal structure shows the two 10S3 ligands arranged in a trans or anti fashion around the mercury center, yielding the meso stereoisomer. Bond distances and angles are very comparable to those found in the structure of the perchlorate salt of the complex cation although the hexafluorophosphate salt shows slightly longer and more varied Hg-S distances (2.623(2), 2.708(2), 2.784(2) Å) with a tetragonal elongation. The 199Hg{1H} NMR spectrum exhibits a single resonance with a chemical shift at -596 ppm consistent with a hexakis(thioether) coordination environment around the mercury center. Crystal data for 1: C2/c, a = 19.184(3) Å, b = 15.235(2) Å, c = 11.3791(15) Å, β = 123.358(2)°, V = 2777.9(6) Å3, Z = 4.
AB - We report the synthesis, crystal structure, and NMR spectroscopy for the mercury(II) complex with the crown thioether 1,4,7-trithiacyclodecane (10S3), bis(1,4,7-trithiacyclodecane)mercury(II) hexafluorophosphate (1). The 10S3 ligand coordinates in tridentate fashion and readily forms a distorted bis octahedral complex, an unusual coordination geometry for Hg(II). The crystal structure shows the two 10S3 ligands arranged in a trans or anti fashion around the mercury center, yielding the meso stereoisomer. Bond distances and angles are very comparable to those found in the structure of the perchlorate salt of the complex cation although the hexafluorophosphate salt shows slightly longer and more varied Hg-S distances (2.623(2), 2.708(2), 2.784(2) Å) with a tetragonal elongation. The 199Hg{1H} NMR spectrum exhibits a single resonance with a chemical shift at -596 ppm consistent with a hexakis(thioether) coordination environment around the mercury center. Crystal data for 1: C2/c, a = 19.184(3) Å, b = 15.235(2) Å, c = 11.3791(15) Å, β = 123.358(2)°, V = 2777.9(6) Å3, Z = 4.
KW - 1,4,7-trithiacyclodecane
KW - Crown thioethers
KW - Mercury NMR
KW - Mercury complexes
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U2 - 10.1023/A:1024954028516
DO - 10.1023/A:1024954028516
M3 - Article
AN - SCOPUS:0042710793
VL - 33
SP - 625
EP - 630
JO - Journal of Crystallographic and Spectroscopic Research
JF - Journal of Crystallographic and Spectroscopic Research
SN - 0277-8068
IS - 8
ER -