Novel polynuclear thallium thiolates with cage structures

Yellow thallium(I)-tetra(2-butanethiolato)-thallium(III) Tl[Tl(SC4H9)4] (1) crystallizes from a solution of thallium(I) carbonate and 2-butanethiol in DMF after heating under reflux in air. In the crystal structure (space group: View the MathML sourceP1¯, a = 8.941(3) Å, b = 11.078(4) Å, c = 13.458(4) Å, α = 70.81(3)°, β = 83.65(3)°, γ = 74.78(3)°, Z = 2) regular, TlS4 tetrahedra are bridged by thallium(I) atoms to an one-dimensional framework. The thallium(I) atoms are in fivefold distorted coordination and are linked to four further TlS4 tetrahedra. The resulting Tl4(S–Bu)8 units consist of two face-sharing Tl3S4 defect cubane entities. TlSC3H7 (2) was obtained from a solution of thallium(I) carbonate and 2-propanethiol in DMF after heating under reflux in air. The crystal structure (space group C2/c, a = 22.501(5) Å, b = 10.360(2) Å, c = 12.760(3) Å, β = 107.92(2)°, Z = 16) contains novel [Tl4(SPr)5]− units which are linked via thallium atoms to one-dimensional molecular chains running parallel to [0 0 1].