Reaction of Bis(N,N-dimethylthiocarbamoyl) Sulfide with Copper(II) Halides and the Crystal and Molecular Structures of Halogeno(bis(N,N-dimethylthiocarbamoyl) sulfido)copper(I) Complexes

Luis I. Victoriano, María Teresa Garland, Andrés Vega

Resultado de la investigación: Article

17 Citas (Scopus)

Resumen

Bis(N,N-dimethylthiocarbamoyl) sulfide (Tetramethylthiuram monosulfide) reacts with copper(II) halides (halide = Cl and Br) to yield 3,5-bis(N,N-dialkyliminio)-1,2,4-trithiolane trihalocuprate(I) and the neutral halogeno(bis-(N,N-dimethylthiocarbamoyl) sulfido)copper(I) complex. The proposed structure for the trihalocuprate(I) compounds is supported mostly by infrared studies. The copper(I) adducts may also be prepared by straightforward reaction of copper(I) halides and the ligand, and single-crystal x-ray studies show a wide diversity of structural variations. All molecules consist of basic S2CuX units. The Cl derivative (1) is an S-bridged dimer (C6H14-ClCuN2OS3, monoclinic, P21/c (No. 14), Z = 4, a = 9.525(8) Å, b = 13.022(10) Å, c = 10.835(7) Å), while the Br analogue (2) features a polymeric network of S2CuBr units, also bridged by S atoms (C6H12BrCuN2S3, orthorhombic, P212121 (No. 19), Z = 4, a = 7.043(2) Å, b = 9.442(3) Å, c = 17.889(4) Å). The iodo compound (3) exists as a halogen-bridged dimer (C6H12CuIN2S3, monoclinic, P21/m (No. 11), Z = 4, a = 9.570(1) Å, b = 10.578(1) Å, c = 12.422(1) Å). The molecular structures found support the assignment of the IR and Raman spectral data in all three cases. The diversity of structural variations is attributed to the relative basicity of the S and halogen potential bridging atoms. Molecular weight studies in acetonitrile are consistent with a monomer for 2, while the temperature dependence of the 1H-NMR for 1 is interpreted in terms of a monomer-dimer equilibrium.

Idioma originalEnglish
Páginas (desde-hasta)688-693
Número de páginas6
PublicaciónInorganic Chemistry
Volumen36
N.º4
EstadoPublished - 12 feb 1997

Huella dactilar

Sulfides
Molecular structure
halides
sulfides
Copper
molecular structure
Crystal structure
Dimers
copper
crystal structure
Halogens
dimers
halogens
monomers
Monomers
Atoms
Alkalinity
adducts
acetonitrile
atoms

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

Citar esto

@article{0fa80774c3444aa086d5d159a3866125,
title = "Reaction of Bis(N,N-dimethylthiocarbamoyl) Sulfide with Copper(II) Halides and the Crystal and Molecular Structures of Halogeno(bis(N,N-dimethylthiocarbamoyl) sulfido)copper(I) Complexes",
abstract = "Bis(N,N-dimethylthiocarbamoyl) sulfide (Tetramethylthiuram monosulfide) reacts with copper(II) halides (halide = Cl and Br) to yield 3,5-bis(N,N-dialkyliminio)-1,2,4-trithiolane trihalocuprate(I) and the neutral halogeno(bis-(N,N-dimethylthiocarbamoyl) sulfido)copper(I) complex. The proposed structure for the trihalocuprate(I) compounds is supported mostly by infrared studies. The copper(I) adducts may also be prepared by straightforward reaction of copper(I) halides and the ligand, and single-crystal x-ray studies show a wide diversity of structural variations. All molecules consist of basic S2CuX units. The Cl derivative (1) is an S-bridged dimer (C6H14-ClCuN2OS3, monoclinic, P21/c (No. 14), Z = 4, a = 9.525(8) {\AA}, b = 13.022(10) {\AA}, c = 10.835(7) {\AA}), while the Br analogue (2) features a polymeric network of S2CuBr units, also bridged by S atoms (C6H12BrCuN2S3, orthorhombic, P212121 (No. 19), Z = 4, a = 7.043(2) {\AA}, b = 9.442(3) {\AA}, c = 17.889(4) {\AA}). The iodo compound (3) exists as a halogen-bridged dimer (C6H12CuIN2S3, monoclinic, P21/m (No. 11), Z = 4, a = 9.570(1) {\AA}, b = 10.578(1) {\AA}, c = 12.422(1) {\AA}). The molecular structures found support the assignment of the IR and Raman spectral data in all three cases. The diversity of structural variations is attributed to the relative basicity of the S and halogen potential bridging atoms. Molecular weight studies in acetonitrile are consistent with a monomer for 2, while the temperature dependence of the 1H-NMR for 1 is interpreted in terms of a monomer-dimer equilibrium.",
author = "Victoriano, {Luis I.} and Garland, {Mar{\'i}a Teresa} and Andr{\'e}s Vega",
year = "1997",
month = "2",
day = "12",
language = "English",
volume = "36",
pages = "688--693",
journal = "Inorganic Chemistry",
issn = "0020-1669",
publisher = "American Chemical Society",
number = "4",

}

TY - JOUR

T1 - Reaction of Bis(N,N-dimethylthiocarbamoyl) Sulfide with Copper(II) Halides and the Crystal and Molecular Structures of Halogeno(bis(N,N-dimethylthiocarbamoyl) sulfido)copper(I) Complexes

AU - Victoriano, Luis I.

AU - Garland, María Teresa

AU - Vega, Andrés

PY - 1997/2/12

Y1 - 1997/2/12

N2 - Bis(N,N-dimethylthiocarbamoyl) sulfide (Tetramethylthiuram monosulfide) reacts with copper(II) halides (halide = Cl and Br) to yield 3,5-bis(N,N-dialkyliminio)-1,2,4-trithiolane trihalocuprate(I) and the neutral halogeno(bis-(N,N-dimethylthiocarbamoyl) sulfido)copper(I) complex. The proposed structure for the trihalocuprate(I) compounds is supported mostly by infrared studies. The copper(I) adducts may also be prepared by straightforward reaction of copper(I) halides and the ligand, and single-crystal x-ray studies show a wide diversity of structural variations. All molecules consist of basic S2CuX units. The Cl derivative (1) is an S-bridged dimer (C6H14-ClCuN2OS3, monoclinic, P21/c (No. 14), Z = 4, a = 9.525(8) Å, b = 13.022(10) Å, c = 10.835(7) Å), while the Br analogue (2) features a polymeric network of S2CuBr units, also bridged by S atoms (C6H12BrCuN2S3, orthorhombic, P212121 (No. 19), Z = 4, a = 7.043(2) Å, b = 9.442(3) Å, c = 17.889(4) Å). The iodo compound (3) exists as a halogen-bridged dimer (C6H12CuIN2S3, monoclinic, P21/m (No. 11), Z = 4, a = 9.570(1) Å, b = 10.578(1) Å, c = 12.422(1) Å). The molecular structures found support the assignment of the IR and Raman spectral data in all three cases. The diversity of structural variations is attributed to the relative basicity of the S and halogen potential bridging atoms. Molecular weight studies in acetonitrile are consistent with a monomer for 2, while the temperature dependence of the 1H-NMR for 1 is interpreted in terms of a monomer-dimer equilibrium.

AB - Bis(N,N-dimethylthiocarbamoyl) sulfide (Tetramethylthiuram monosulfide) reacts with copper(II) halides (halide = Cl and Br) to yield 3,5-bis(N,N-dialkyliminio)-1,2,4-trithiolane trihalocuprate(I) and the neutral halogeno(bis-(N,N-dimethylthiocarbamoyl) sulfido)copper(I) complex. The proposed structure for the trihalocuprate(I) compounds is supported mostly by infrared studies. The copper(I) adducts may also be prepared by straightforward reaction of copper(I) halides and the ligand, and single-crystal x-ray studies show a wide diversity of structural variations. All molecules consist of basic S2CuX units. The Cl derivative (1) is an S-bridged dimer (C6H14-ClCuN2OS3, monoclinic, P21/c (No. 14), Z = 4, a = 9.525(8) Å, b = 13.022(10) Å, c = 10.835(7) Å), while the Br analogue (2) features a polymeric network of S2CuBr units, also bridged by S atoms (C6H12BrCuN2S3, orthorhombic, P212121 (No. 19), Z = 4, a = 7.043(2) Å, b = 9.442(3) Å, c = 17.889(4) Å). The iodo compound (3) exists as a halogen-bridged dimer (C6H12CuIN2S3, monoclinic, P21/m (No. 11), Z = 4, a = 9.570(1) Å, b = 10.578(1) Å, c = 12.422(1) Å). The molecular structures found support the assignment of the IR and Raman spectral data in all three cases. The diversity of structural variations is attributed to the relative basicity of the S and halogen potential bridging atoms. Molecular weight studies in acetonitrile are consistent with a monomer for 2, while the temperature dependence of the 1H-NMR for 1 is interpreted in terms of a monomer-dimer equilibrium.

UR - http://www.scopus.com/inward/record.url?scp=0001350438&partnerID=8YFLogxK

M3 - Article

AN - SCOPUS:0001350438

VL - 36

SP - 688

EP - 693

JO - Inorganic Chemistry

JF - Inorganic Chemistry

SN - 0020-1669

IS - 4

ER -