Pseudopolymeric Thallium(I) Di-iso-pentyl Dithiophosphate, [Tl{S2P(O-iso-С5H11)2}]: Synthesis, Structural Organization (Role of Secondary Tl⋅⋅⋅S and Tl⋅⋅⋅O Interactions in Supramolecular Self-Assembly), and Thermal Behavior

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Abstract

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.

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About the authors

O. A. Bredyuk

Institute of Geology and Nature Management, Far Eastern Branch, Russian Academy of Sciences

Email: alexander.v.ivanov@chemist.com
Russian Federation, Blagoveshchensk

I. A. Lutsenko

Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences

Email: alexander.v.ivanov@chemist.com
Russian Federation, Moscow

Yu. V. Nelyubina

Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences

Email: alexander.v.ivanov@chemist.com
Russian Federation, Moscow

S. V. Zinchenko

Favorsky Institute of Chemistry, Siberian Branch, Russian Academy of Sciences

Email: alexander.v.ivanov@chemist.com
Russian Federation, Irkutsk

A. V. Ivanov

Institute of Geology and Nature Management, Far Eastern Branch, Russian Academy of Sciences

Author for correspondence.
Email: alexander.v.ivanov@chemist.com
Russian Federation, Blagoveshchensk

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Supplementary files

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2. Fig. 1. Packing of molecular structural units in crystal I

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3. Fig. 2. Non-equivalent molecules of complex I: A with Tl(1) and Tl(1)´ atoms (a, b) and B (c). Ellipsoids of 50% probability

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4. Fig. 3. Method of construction of supramolecular pseudopolymer chains by molecules A (a) and B (b). Intermolecular secondary interactions Tl---S and Tl---O are shown in dotted lines; symmetry transformations: a x, 3/2 - y, ½ + z; b x, 3/2 - y, -½ + z. Alkyl substituents are not given

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5. Fig. 4. Joining of neighbouring pseudopolymer chains to form a double supramolecular ribbon. All non-equivalent secondary interactions realised between the chains are given. Symmetric transformations: a x, 3/2 - y, ½ + z; b x, 3/2 - y, -½ + z

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6. Fig. 5. TG (a) and DSC (b) curves; size and shape of I crystals (c)

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7. Fig. 6. Enlarged fragment of the crucible bottom with residual substance after thermolysis I (a), size, shape and microstructure of substance particles (b) and its energy-dispersive spectrum (c)

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