The Crystal and Molecular Structure of Silver(I) N,N-Diethyldithiocarbamate

Abstract

The crystal structure of silver (I) N,N-diethyldithiocarbamate was determined by the X-ray diffraction method. The crystals are monoclinic, with the space group P21/c, and with two hexameric molecules in a unit cell with dimensions of a=10.90±0.02, b=24.72±0.01, c=11.51±0.02 Å, and β=125.8±0.1°. The structure was solved by a heavy-atom method and was refined by block-diagonal least-squares methods to a final R-value of 0.029 for 2108 observed reflections. The structure consists of hexameric molecules, [AgS2CN(C2H5)2]6. The hexameric structure was essentially consistent with Hesse’s preliminary result (1960). The terminal silver atom in one molecule is bridged by a sulfur atom to that in the adjacent hexamer, forming a chain structure along the a axis. All the silver atoms are connected to five atoms (either 1Ag and 4S or 2Ag and 3S). The dithiocarbamate ligands are classified into three types: bidentate, intra-, and inter-molecule tetradentate.

Insights into the Synthesis Mechanism of Ag29 Nanoclusters

“…53 The spectrum of Ag 29 resembles somewhat that of the Ag(I)-thio and Ag 2 S, in particular the former. The structure of Ag(I)-thio has been shown to consist of bridged hexameric units [AgS 2 CN(C 2 H 5 ) 2 ] 6 where each Ag atom is connected to either 1 Ag and 4 S or 2 Ag and 3 S. 54 It is thus not unreasonable to compare this to the surface atoms of the Ag clusters. We further observe that the strong whiteline of AgNO 3 does not appear in the Ag 29 spectrum.…”

Synthesis, Crystal Structures, Magnetic Properties and Photoconductivity of C60 and C70 Complexes with Metal Dialkyldithiocarbamates M(R2dtc)x, where M = CuII, CuI, AgI, ZnII, CdII, HgII, MnII, NiII, and PtII; R = Me, Et, and nPr

“…[47,48] and for Ag I (Et 2 dtc) hexamers and polymers are also known. [49,50] According to the best of our knowledge, a tetrameric structure is for the first time observed for Cu I (Et 2 dtc). Probably, the formation of complexes with C 60 and C 70 stabilizes the tetrameric structure.…”

Bis(μ-N,N-diethyldithiocarbamato-κ3S,S′:S′)bis[(μ-N,N-diethyldithiocarbamato-κ2S,S′)silver(II)]

“…Ag I compounds incorporating dialkyldithiocarbamate have been widely studied (Yamaguchi et al, 1976;Hesse & Nilson, 1969). The partial oxidation product [Ag 6 (detc) 4 (SCN) 4 ] (detc = N,N-diethyldithiocarbamate) was prepared by the reaction of the Ag I compound [Ag(detc)] 6 and (SCN) 2 at room temperature (Calabro et al, 1981).…”