Models of lysine-cysteine hydrogen bonding in metallothionein

Hydrogen bonding between ammonium and benzenethiolate in [(C6H11)2NH2]2[Co(SC 6H5)4]

Wesley P. Chung, John C. Dewan, Marc Walters

Research output: Contribution to journalArticle

Abstract

Anion-cation hydrogen bonding interactions are described for [(C6H11)2NH2]2[M(SC 6H5)4] where M = Co (1), Zn (3), which serve as models of putative lysine-cyteine hydrogen bonding at the metal binding site of metallothionein. Complex 1 is isolated as green crystals in which an average N-H⋯S hydrogen bond length of 3.29 (1) Å is observed in infinite one-dimensional chains. The dicyclohexylammonium counterion occupies a bridging position by hydrogen bonding to thiolate ligand sulfur atoms on adjacent anion complexes. There are two [Co(SC6H5)4]2- anions per asymmetric unit where each Co atom is tetrahedrally coordinated by four benzenethiolate ligands [Co-Sav = 2.308 (4) Å]. In the non-hydrogen bonding complex [(CH3)4N]2-[Co(SC6H 5)4] (5), a split vibrational band at 228 cm-1 (av) is assigned to a Co-S T2 related mode. In [(CH3)4N]2[Zn(SC6H5) 4] (7) this band is replaced by one at 199 cm-1. Relatively intense bands at 192 and 180 cm-1 in the Raman spectra of 1 and 3 are assigned to metal-ligand modes. Hydrogen bonding causes a decrease in metal-ligand bond length of 0.02 Å relative to the bonds in a non-hydrogen bonding complex.

Original languageEnglish (US)
Pages (from-to)525-530
Number of pages6
JournalJournal of the American Chemical Society
Volume113
Issue number2
StatePublished - Jan 16 1991

Fingerprint

Metallothionein
Hydrogen Bonding
Ammonium Compounds
Lysine
Cysteine
Hydrogen bonds
Ligands
Anions
Metals
Negative ions
Bond length
Atoms
Sulfur
Chemical bonds
Cations
Hydrogen
Binding sites
Binding Sites
Raman scattering
Positive ions

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

@article{1fb078ad2fec44bf88f789955821fc62,
title = "Models of lysine-cysteine hydrogen bonding in metallothionein: Hydrogen bonding between ammonium and benzenethiolate in [(C6H11)2NH2]2[Co(SC 6H5)4]",
abstract = "Anion-cation hydrogen bonding interactions are described for [(C6H11)2NH2]2[M(SC 6H5)4] where M = Co (1), Zn (3), which serve as models of putative lysine-cyteine hydrogen bonding at the metal binding site of metallothionein. Complex 1 is isolated as green crystals in which an average N-H⋯S hydrogen bond length of 3.29 (1) {\AA} is observed in infinite one-dimensional chains. The dicyclohexylammonium counterion occupies a bridging position by hydrogen bonding to thiolate ligand sulfur atoms on adjacent anion complexes. There are two [Co(SC6H5)4]2- anions per asymmetric unit where each Co atom is tetrahedrally coordinated by four benzenethiolate ligands [Co-Sav = 2.308 (4) {\AA}]. In the non-hydrogen bonding complex [(CH3)4N]2-[Co(SC6H 5)4] (5), a split vibrational band at 228 cm-1 (av) is assigned to a Co-S T2 related mode. In [(CH3)4N]2[Zn(SC6H5) 4] (7) this band is replaced by one at 199 cm-1. Relatively intense bands at 192 and 180 cm-1 in the Raman spectra of 1 and 3 are assigned to metal-ligand modes. Hydrogen bonding causes a decrease in metal-ligand bond length of 0.02 {\AA} relative to the bonds in a non-hydrogen bonding complex.",
author = "Chung, {Wesley P.} and Dewan, {John C.} and Marc Walters",
year = "1991",
month = "1",
day = "16",
language = "English (US)",
volume = "113",
pages = "525--530",
journal = "Journal of the American Chemical Society",
issn = "0002-7863",
publisher = "American Chemical Society",
number = "2",

}

TY - JOUR

T1 - Models of lysine-cysteine hydrogen bonding in metallothionein

T2 - Hydrogen bonding between ammonium and benzenethiolate in [(C6H11)2NH2]2[Co(SC 6H5)4]

AU - Chung, Wesley P.

AU - Dewan, John C.

AU - Walters, Marc

PY - 1991/1/16

Y1 - 1991/1/16

N2 - Anion-cation hydrogen bonding interactions are described for [(C6H11)2NH2]2[M(SC 6H5)4] where M = Co (1), Zn (3), which serve as models of putative lysine-cyteine hydrogen bonding at the metal binding site of metallothionein. Complex 1 is isolated as green crystals in which an average N-H⋯S hydrogen bond length of 3.29 (1) Å is observed in infinite one-dimensional chains. The dicyclohexylammonium counterion occupies a bridging position by hydrogen bonding to thiolate ligand sulfur atoms on adjacent anion complexes. There are two [Co(SC6H5)4]2- anions per asymmetric unit where each Co atom is tetrahedrally coordinated by four benzenethiolate ligands [Co-Sav = 2.308 (4) Å]. In the non-hydrogen bonding complex [(CH3)4N]2-[Co(SC6H 5)4] (5), a split vibrational band at 228 cm-1 (av) is assigned to a Co-S T2 related mode. In [(CH3)4N]2[Zn(SC6H5) 4] (7) this band is replaced by one at 199 cm-1. Relatively intense bands at 192 and 180 cm-1 in the Raman spectra of 1 and 3 are assigned to metal-ligand modes. Hydrogen bonding causes a decrease in metal-ligand bond length of 0.02 Å relative to the bonds in a non-hydrogen bonding complex.

AB - Anion-cation hydrogen bonding interactions are described for [(C6H11)2NH2]2[M(SC 6H5)4] where M = Co (1), Zn (3), which serve as models of putative lysine-cyteine hydrogen bonding at the metal binding site of metallothionein. Complex 1 is isolated as green crystals in which an average N-H⋯S hydrogen bond length of 3.29 (1) Å is observed in infinite one-dimensional chains. The dicyclohexylammonium counterion occupies a bridging position by hydrogen bonding to thiolate ligand sulfur atoms on adjacent anion complexes. There are two [Co(SC6H5)4]2- anions per asymmetric unit where each Co atom is tetrahedrally coordinated by four benzenethiolate ligands [Co-Sav = 2.308 (4) Å]. In the non-hydrogen bonding complex [(CH3)4N]2-[Co(SC6H 5)4] (5), a split vibrational band at 228 cm-1 (av) is assigned to a Co-S T2 related mode. In [(CH3)4N]2[Zn(SC6H5) 4] (7) this band is replaced by one at 199 cm-1. Relatively intense bands at 192 and 180 cm-1 in the Raman spectra of 1 and 3 are assigned to metal-ligand modes. Hydrogen bonding causes a decrease in metal-ligand bond length of 0.02 Å relative to the bonds in a non-hydrogen bonding complex.

UR - http://www.scopus.com/inward/record.url?scp=0026032657&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0026032657&partnerID=8YFLogxK

M3 - Article

VL - 113

SP - 525

EP - 530

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

SN - 0002-7863

IS - 2

ER -