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 2 CNC 5 H 10 ) 3 ] and [In(η 2 ‐pyS) 3 ]

The η 2 ‐thio‐indium complexes [In(η 2 ‐thio) 3 ] (thio = S 2 CNC 5 H 10 , 2 ; SNC 4 H 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 2 CNC 5 H 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) Å, b = 12.1821(7) Å, c = 16.0893(10) Å, β = 101.654(1)°, V = 2600.9(3) Å 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) Å, b = 11.7047 (8) Å, c = 9.4046 (7) Å, β = 114.78 (1)°, V = 880.13(11) Å 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) Å in 2 and C‐S bond length in the range of 1.715(2)–1.753(6) Å in 2 and 3 , respectively, indicate considerable partial double bond character.