Novel polynuclear thallium thiolates with cage structures

• Published in: Inorganica Chimica Acta 2005-11, Vol.358 (14), p.4247-4252
• Main Authors: Hammerschmidt, Adrienne, Brömmelhaus, Andreas, Läge, Mechtild, Krebs, Bernt
• Format: Article
• Language: English
• Subjects: Crystal structures; Mixed valence; Thallium; Thiolates
• ISSN: 0020-1693; 1873-3255
• DOI: 10.1016/j.ica.2005.03.038

In the novel mixed-valent thallium thiolate Tl[Tl(S 2C 4H 9) 4], Tl 4(S–Bu) 8 units exhibit interesting face-sharing Tl 3S 4 defect cubane entities. Yellow thallium(I)-tetra(2-butanethiolato)-thallium(III) Tl[Tl(SC 4H 9) 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: P 1 ¯ , 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, TlS 4 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 TlS 4 tetrahedra. The resulting Tl 4(S–Bu) 8 units consist of two face-sharing Tl 3S 4 defect cubane entities. TlSC 3H 7 (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 [Tl 4(SPr) 5] − units which are linked via thallium atoms to one-dimensional molecular chains running parallel to [0 0 1].