Synthesis, crystal structure and spectroscopic properties of diarganothallium (III) derivatives of 2,6-diacetyl-pyridine-monothiosemicarbazone

• Published in: Polyhedron Vol. 17; no. 13; pp. 2249 - 2256
• Main Authors: Casas, J.S., Castellano, E.E., García-Tasende, M.S., Sánchez, A., Sordo, J., Vidarte, M.J.
• Format: Journal Article
• Language: English
• Published: Elsevier Ltd 1998
• Subjects: crystal structure; diorganothallium complexes; thallium complexes; thiosemicarbazone complexes; diorganothallium complexes; crystal structure; thallium complexes; thiosemicarbazone complexes
• ISSN: 0277-5387
• DOI: 10.1016/S0277-5387(98)00035-7

Dimethyl(2,6-diacetyl-pyridine-monothiosemicarbazonato)thallium(III), [TlMe 2(L)], and Diphenyl-(2,6-diacetyl-pyridine-monothiosemicarbazonato)thallium(III) chloroform solvate, [TlPh 2(L)],CHCl 3 were prepared by reacting the corresponding diorganothallium(III) hydroxide with 2,6-diacetyl-pyridinemonothiosemicarbazone (HL). [TlMe 2(L)] crystallizes in the triclinic space group P l (no. 2) with a = 7.064(3), b = 9.149(2), c = 12.377(2) A ̊ , α = 79.378(11), β = 74.92(2), γ = 82.75(2)°, Z = 2, R 1 = 0.0305, Rw 2 = 0.0673 . [TlPh 2(L)].CHCl 3 crystallizes in the monoclinic space group C2/ c with a = 23.559(3), b = 13.582(2), c = 16.808(3) A ̊ , β = 106.04(1)°, Z = 8, R 1 = 0.0620, Rw 2 = 0.1155 . Both complexes consist of molecules in which the deprotonated ligand is S,N(3),N(4),O-bonded to the thallium atom [TlMe 2(L)], Tl S = 2.872(2), Tl N(3) = 2.590(6), Tl N(4) = 2.686(2), Tl O = 2.883(6) A ̊ ; [TlPh 2(L).CHC] 3, Tl S = 2.791(6), Tl N(4) = 2.579(14), Tl O = 2.86(1) A ̊ ]. A weak bond Tl…O′ [TlMe 2(L)], 3.050(2) Å; [TlPh 2(L)].CHCl 3, 3.42(1) Å] between neighbouring molecules give rise to weakly bonded dimers. The 1H, 13C and 205Tl NMR spectra of both compounds in DMSO indicate that the bonding scheme observed in solid state is only partially retained in solution, where at least two isomers are observed.