Complexes of 1-methyl-4-mercaptopiperidine with zinc(II), cadmium(II) and mercury(II) halides

doi:10.1016/S0277-5387(00)80978-X

Polyhedron

Volume 1, Issue 2, 1982, Pages 157-161

https://doi.org/10.1016/S0277-5387(00)80978-X Get rights and content

Abstract

The preparation of a series of complexes formed by 1-methyl-4-mercaptopiperidine (AH) and divalent zinc, cadmium and mercury halides is reported together with some spectral and physical properties. The results of a crystallographic study allows to establish the structure of those of formula [M₂(AH)₂X₄]H₂O (M = Zn, Cd, Hg; X = Br, I) consisting of dimers and involving tetrahedral environment with sulphur-bridges for the metal atoms. Polymeric structures are proposed for the complexes of formulae Cd(AH)Cl₂ and Hg₂Cl₄(AH).

References (17)

W.J. Geary
Coord. Chem. Rev.
(1971)
J.C. Bayón et al.
Inorg. Chem.
(1979)
M.C. Briansó et al.
J. Chem Soc. Dalton Trans.
(1981)
D.C. Bradley et al.
J. Chem. Phys.
(1964)
N.R. Kunchur
Nature
(1964)
D.C. Bradley et al.
Can. J. Chem.
(1965)
D. Grdenić
Quart. Rev.
(1965)
H. Barrera et al.
J. Org. Chem.
(1962)

There are more references available in the full text version of this article.

Cited by (18)

Synthetic and structural chemistry of groups 11 and 12 metal complexes of the zwitterionic ammonium thiolate ligands
2008, Coordination Chemistry Reviews
The chemistry of metal complexes of the zwitterionic ammonium thiolates has expanded dramatically in the recent years. This review is intended to summarize the synthesis and crystal structures of groups 11 and 12 metal zwitterionic ammonium thiolate complexes. Seven methods for the synthesis of these metal complexes of the zwitterionic ammonium thiolates are outlined: proton transfer reaction, precursor reaction, ligand exchange reaction, oxidation–reduction reaction, solid-state reaction, electrochemical reaction and hydro(solvo)thermal reaction. These metal complexes of the zwitterionic ammonium thiolates are classified according to the number of metal atoms; their specific structures are briefly discussed.
Schiff bases derived from mercury(II)-aminothiolate complexes as metalloligands for transition metals
2001, Journal of Organometallic Chemistry
Mercury(II) complexes of aromatic aminothiolate ligands of formula [Hg(n-SC₆H₄NH₂)₂], n=3 (1) or 4 (2) and [RHg(n-SC₆H₄NH₂)], R=Me, n=3 (3) or 4 (4); R=Ph, n=3 (5) or 4 (6) have been obtained and characterized by infrared and ¹H, ¹³C and ¹⁹⁹Hg-NMR spectroscopies. The latter indicates that, in solution, complexes 1–6 have an essentially linear coordination about Hg(II). Unprecedented Schiff bases containing the Hg–S(thiolate) bond have been synthesized from 3–6 and salicylaldehyde yielding complexes of formula [RHg(n-SC₆H₄NCHC₆H₄OH)], R=Me, n=3 (7) or 4 (8); R=Ph, n=3 (9) or 4 (10). The template reaction of 3 and 4 with M(CH₃COO)₂, M=Zn(II), Cd(II), and salicylaldehyde has afforded trimetallic complexes of formula [M^II{MeHg(n-SC₆H₄NCHC₆H₄O)}₂], M=Zn, n=3 (11) or 4 (12); M=Cd, n=3 (13) or 4 (14). Complexes 7–14 have also been explored by use of infrared and NMR spectroscopies. The crystal structure determination of 2, 3, 5, 7 and 8 by X-ray diffraction shows that Hg(II) has an essentially linear coordination. The presence of additional secondary Hg⋯S interactions in all these complexes leads to an increase in the coordination number of Hg to 4 or 5. In 2, the interaction of each S–Hg–S unit with three neighbouring units gives rise to a polymeric chain, which can be considered as being formed by pairs of fused incomplete cubanes. In 3, 5, 7 and 8, secondary Hg⋯S bonds between pairs of C–Hg–S fragments yield Hg₂S₂ dimers. In 3, these dimers afford two-dimensional sheets by means of additional Hg⋯N secondary interactions. The crystal packing of the Hg₂S₂ dimers in 5, 7 and 8 is very similar and gives rise to one-dimensional chains by means of additional Hg⋯S bonds. The resulting polymeric zig-zag ladders can be described as formed by Hg₄S₄ pseudo-cubanes sharing opposite faces.
Preparation of complexes of the 3-trimethylammonio-1-propanethiolato ligand, [M{S(ÇH<inf>2</inf>)<inf>3</inf>NMe<inf>3</inf>}<inf>2</inf>](PF<inf>6</inf>)<inf>2</inf>, M=Zn, Cd, Hg. Crystal structures of monomeric and polymeric forms of the mercury complex
1991, Inorganica Chimica Acta
Reaction of metal acetates with 3-trimethylammonio-1-propanethiol hexafluorophosphate [HS(CH₂)₃NMe₃](PF₆) in a methanol-acetonitrile-aqueous sodium hydroxide solution gives complexes of formula [M{S(CH₂)₃NMe₃}₂](PF₆)₂ (M=Zn, Cd, Hg) as crystalline or microcrystalline solids. In the case of mercury, an alternative product, [M{S(CH₂)₃NMe₃}₂](PF₆)₂· $12$ [S(CH₂)₃NMe₃] is sometimes obtained instead, from an apparently identical procedure. The crystal structures of both mercury complexes have been determined. [Hg{S(CH₂)₃NMe₃}₂](PF₆)₂· $12$ [S(CH₂)₃NMe₃] contains polymeric chains of mercury atoms bridged by pairs of aminothiolato ligands to give tetrahedral coordination with Hg-S 2.564(3) and 2.567(3) Å. The cation chains run parallel to the tetragonal unit cell c axis and are separated by PF₆⁻ anions. Channels in the structure are probably occupied by the disordered additional ligand molecules in zwitterionic form. [Hg{S(CH₂)₃NMe₃}₂](PF₆)₂ contains essentially linear mononuclear cations with Hg-S 2.321(9)–2.370(11) Å, which are linked by weaker Hg…S interactions (2.98–3.59 Å) into loose octameric cation units. These are widely separated from each other by the surrounding anions.
Mercury-sulphur stretching frequencies, synthesis and x-ray crystal structure of catena-μ-(3-dimethylammonio-1-propanethiolato)dichloromercury(II)
1988, Polyhedron
The crystal structure of the title compound has been determined. Crystals of [HgC1₂{μ-S(CH₂)₃NH(CH₃)₂}] are monoclinic, space group P2₁/n, with a = 10.136(2), b = 6.519(1), c = 15.940(6) Å and β = 97.20(3)°. The structure consists of (HgS)_n helicoidal chains linked by hydrogen bonding, which give rise to chemically unconnected layers along the (2̄02) planes. Each mercury is tetrahedrally coordinated to two terminal chlorine atoms and two bridging sulphur atoms. Assignments of ν_as(SHgS) and ν_s(SHgS) for this complex and its isostructural bromine analogue, and of ν_s(C1HgC1) and ν_s(BrHgBr) from IR and Raman spectroscopy are reported. Comparison of HgS frequencies with those reported for closely related compounds as well as correlation with HgS bond distances are made.
Synthesis, structure and properties of syn-bis(μ-N-methylpiperidine-4-thiolate tricarbonyl iron)
1986, Inorganica Chimica Acta
The reaction of Fe₃(CO)₁₂ with N-methyl-4- mercaptopiperidine gives the title compound. Crystals are monoclinic, space group P2₁/c with a = 12.922(2), b = 14.784(5), c = 13.607(2) Å, β = 112.41(1)°. With Z = 4 the calculated density is 1.49 g cm⁻³. Solution of the structure by direct methods led to a final weighted R factor of 0.029 for 2270 independent reflections. The FeFe bond length is 2.534(1) Å and the S···S distance of 2.940(1) suggests bonding interactions. By heating upon reflux in toluene during 10 h, the IR spectrum of the chromatographed solution indicates the syn isomer formation. The reaction with CH₃I and HClO₄ produces the methylation and protonation, respectively, of the nitrogen atoms of the piporidine rings giving rise to the formation of the [Fe(μ-(CH₃)₂NC₅H₉S)(CO)₃]₂I₂·2H₂O and [Fe(μ-HCH₃NC₅H₉S)(CO)₃]₂·H₂O·CH₃OH compounds.
Complexes of heterocyclic thione donors
1985, Coordination Chemistry Reviews

View all citing articles on Scopus

View full text

Complexes of 1-methyl-4-mercaptopiperidine with zinc(II), cadmium(II) and mercury(II) halides

Abstract

Coord. Chem. Rev.

Inorg. Chem.

J. Chem Soc. Dalton Trans.

J. Chem. Phys.

Nature

Can. J. Chem.

Quart. Rev.

J. Org. Chem.