Dialkyldithiocarbamate platinum(II) complexes of [Pt(S 2 CNR 2 ) 2 ] (R =  iso -C 3 H 7 ,  iso -C 4 H 9 ): Preparation,  13 C CP-MAS NMR, molecular structure, supramolecular self-assembly and thermal behaviour

Two new dialkyldithiocarbamato platinum(II) complexes of [Pt(S 2 CNR) 2 ], R = iso -C 3 H 7 ( 1 ) and iso -C 4 H 9 ( 2 ), have been prepared and characterised using 13 C CP-MAS NMR. The crystal and molecular structures of the isolated compounds were established by single-crystal X-ray diffraction. The unit cell of 1 contains four centrosymmetric discrete molecules of [Pt{S 2 CN( iso -C 3 H 7 ) 2 } 2 ], of which the pairs are structurally inequivalent to each other (hereafter denoted as molecules 1a and 1b ). At the supramolecular level, due to numerous intermolecular C–H···S hydrogen bonds, the 1a molecules form linear polymeric ribbons, whose interaction with the 1b molecules results in a two-dimensional polymeric network. In the structure of 2 , the construction of supramolecular zigzag chains by non-centrosymmetric molecules of [Pt{S 2 CN( iso -C 4 H 9 ) 2 } 2 ] is determined by intermolecular C–H···Pt anagostic interactions. The thermal behaviour of crystalline compounds 1 and 2 was studied by simultaneous thermal analysis (STA), a combination of the TG and DSC techniques, under an argon atmosphere. In both cases, platinum(II) sulphide (PtS) was identified as the main end-product upon thermal decomposition of the complexes at 600 °C.