Pseudopolymeric Thallium(I) Di-<i>iso</i>-pentyl Dithiophosphate, [Tl{S<sub>2</sub>P(O-<i>iso</i>-С<sub>5</sub>H<sub>11</sub>)<sub>2</sub>}]: Synthesis, Structural Organization (

Crystalline pseudopolymeric thallium(I) di-iso-pentyl dithiophosphate (Dtph), [Tl{S2P(O-iso-С5H11)2}] (I), is synthesized and characterized in detail by single-crystal XRD (CIF file CCDC no. 2296421), simultaneous thermal analysis (STA), multinuclear (1H, 13C, 31P) NMR and IR spectroscopy. Nonequivalent molecules of two types containing Tl(1) and Tl(2) atoms (hereinafter molecules А and В, respectively) are involved (1 : 1) in the formation of the structure of compound I. In both molecules, the S,S´-anisobidentate coordination of the Dtph ligands (Tl–S bond lengths 3.006–3.092 Å) results in the formation of small-size four-membered metallocycles [TlS2P] (a 'butterfly' conformation) with significantly averaged P–S bond lengths (1.966–1.985 Å). Molecules A and B are structurally ordered upon the construction of supramolecular chains of two types (⋅⋅⋅A⋅⋅⋅A⋅⋅⋅A⋅⋅⋅)n and (⋅⋅⋅B⋅⋅⋅B⋅⋅⋅B⋅⋅⋅)n with oppositely directed structural units combined by paired secondary Tl⋅⋅⋅S and Tl⋅⋅⋅O interactions alternating over the chain length. In turn, paired secondary (but weaker) Tl⋅⋅⋅S interactions occur between molecules A and B belonging to two neighboring pseudopolymeric chains. The multiplisity of these interactions provides the formation of double supramolecular ribbons. The thermal behavior of compound I is studied by the STA technique under an argon atmosphere. Thallium(I) tetrathiophosphate Tl3PS4 is identified as the only end product of the thermolysis of compound I. Electron probe microanalysis (EPMA) and scanning electron microscopy (SEM) are used to study the residual substance.