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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.

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