Syntheses, and Crystal Structures of Indium Complexes with η~2-Piperidinyldithiocarbamate and η~2-Pyridine-2-thionate Containing Ligands: Structures of [In(η~2-S_2CNC_5H_(10))_3] and [In(η~2-pyS)_3]

摘要

The η~2-thio-indium complexes [In(η~2-thio)_3] (thio = S_2CNC_5H_(10), 2; SNC_4H_4, (pyridine-2-thionate, pyS, 3) and [In(η~2-pyS)_2(η~2-acac)], 4, (acac: acetylacetonate) are prepared by reacting the tris(η~2-acac)indium complex [In(η~2-acac)_3], 1 with HS_2CNC_5H_(10), pySH, and pySH with ratios of 1:3, 1:3, and 1:2 in dichloromethane at room temperature, respectively. All of these complexes are identified by spectroscopic methods and complexes 2 and 3 are determined by single-crystal X-ray diffraction. Crystal data for 2: space group, C2/c with a = 13.5489(8) A, b = 12.1821(7) A, c = 16.0893(10) A, β = 101.654(1)°, V = 2600.9(3) A~3, and Z = 4. The structure was refined to R = 0.033 and Rw = 0.086; Crystal data for 3: space group, P2_1 with a = 8.8064 (6) A, b = 11.7047 (8) A, c = 9.4046 (7) A, β = 114.78 (1)°, V = 880.13(11) A~3, and Z = 2. The structure was refined to R = 0.030 and Rw = 0.061. The geometry around the metal atom of the two complexes is a trigonal prismatic coordination. The piperidinyldithiocarbamate and pyridine-2-thionate ligands, respectively, coordinate to the indium metal center through the two sulfur atoms and one sulfur and one nitrogen atoms, respectively. The short C-N bond length in the range of 1.322(4)-1.381(6) A in 2 and C-S bond length in the range of 1.715(2)-1.753(6) A in 2 and 3, respectively, indicate considerable partial double bond character.