X-Ray crystal structures and properties of tris(tetrathiafulvalenium) tetrachlorodimethylstannate(IV) and tetrathiafulvalenium trichlorodimethylstannate(IV)

Abstract

A single-crystal X-ray structure analysis has been performed for [ttf]₃[SnMe₂Cl₄] obtained by electrocrystallization of tetrathiafulvalene (ttf) in the presence of SnMe₂Cl₂ and [NEt₄]Cl in acetonitrile. The crystals are tetragonal, space group P4/mbm, with Z= 2, a= 11.725(1), and c= 12.194(3)Å. Block-diagonal least-squares refinement, based on 847 independent reflections with |F₀| > 3σ(F), converged at R= 0.052. The ttf molecules exist as trimers, located perpendicularly to each other, forming a two-dimensional network with somewhat close sulphur–sulphur contacts among the trimers. The [SnMe₂Cl₄]^2– anions are disordered with respect to the Sn–Me and Sn–Cl bonds. An X-ray structure analysis of [ttf][SnMe₂Cl₃] obtained by the reaction of [ttf]₃[BF₄]₂ with SnMe₂Cl₂ and [NEt₄]Cl in acetonitrile has shown that both ttf ˙⁺ radical cations and [SnMe₂Cl₂]^–anions exist as dimers. The crystals are triclinic, space group P, with cell dimensions a= 9.348(1), b= 10.475(1), c= 8.451 7(9)Å, α= 92.47(1), β= 102.53(1), γ= 109.27(1)°, and Z= 2. Least-squares refinement, based on 3 196 independent reflections with |F_o| > 3σ(F), converged at R= 0.048.