Synthesis, characterization, and crystal structure of µ-[1′-pyrrolidinecarbodithioato-S(Bi1,2)S′(Bi2)]-1,1,1,2,2-pentakis(1′-pyrrolidinecarbodithioato-SS′)dibismuth(III) ethanol (1/1) and of di-µ-chloro-bis[bis(1-pyrrolidinecarbodithioato-SS′)(thiourea-S)bismuth(III)]

Abstract

Reaction of BiCl₃ and ammonium 1-pyrrolidinecarbodithioate, [NH₄]pcdt, in CH₂Cl₂–EtOH (1 : 1) gave [{Bi(pcdt)₃}₂]·EtOH (1). Grinding BiCl₃ and thiourea (tu) and reacting with [NH₄]pcdt in CH₂Cl₂–EtOH (1 : 1) gave [{Bi(tu)(pcdt)₂Cl}₂](2). Compounds (1) and (2) have been characterized by single-crystal X-ray diffraction: both are triclinic, space group P, with for (1), a= 15.907(7), b= 14.429(7), c= 11.253(6)Å, α= 82.84(8), β= 84.55(9), γ= 81.02(9)°, Z= 2 and R= 0.065. For (2), a= 10.491(6), b= 11.335(8), c= 8.81 2(7)Å, α= 102.58(8), β= 107.44(6), γ= 97.44(8)°, Z= 1, and R= 0.028. In (1) the co-ordination around one bismuth atom is trigonal prismatic with an extraposition on a rectangular face, and pentagonal pyramidal around the other bismuth atom; a sulphur atom joins the two polyhedra with an asymmetric bridge. In (2) co-ordination at bismuth is pentagonal bipyramidal; two chlorines, one apical and one equatorial, are bridging so that two adjacent polyhedra share an edge.