Ionische Kronenetherkomplexe von Thallium(I), Blei(II) und Indium(III). Die Kristallstrukturen von [T1(12-Krone-4)₂] [SbC₆], [Pb(15-Krone-5)₂] [SbCl₆]₂ • [SbCl₃(15-Krone-5)] und [In(12-Krone-4)₂] [SbCl₆]₃· 3 CH₃CN / Ionic Crown Ether Complexes of Thallium(I), Lead(II), and Indium(III). Crystal Structures of [T1(12-Crown-4)₂][SbCl₆], [Pb(15-Crown-5)₂] [SbCl₆]₂ • [SbCl₃(15-Crown-5)], and [In(12-Crown-4)₂] [SbCl₆]₃ · 3 CH₃CN

Abstract

The ionic crown ether complexes [Tl(12-crown-4) 2 ][SbCl 6 ] (1) and [In(12-crown-4)2][SbCl 6 ] 3 ·3 CH 3 CN (3) have been prepared by reaction of T1C1 and InCl 3 , respectively, with SbCl 5 in the presence of 12-crown-4 in acetonitrile solution. The lead complex [Pb(15-crown-5) 2 ][SbCl 6 ] 2 · [SbCl 3 (15-crown-5)] (2) has been obtained from the reaction of Pb(CH 3 ) 2 Cl 2 with SbCl 5 in the presence of 15-crown-5 in acetonitrile solution. 1-3 were characterized by crystal structure determinations. [Tl(12-crown-4) 2 ][SbCl 6 ] (1): Space group C2/c, Z = 4, 2306 observed unique reflections, R = 0.051. Lattice dimensions at -70°C: a = 2360.9(5), b = 1189.6(2), c = 1080.4(3) pm, β = 111.14(2)°. 1 contains cations [Tl(12-crown-4) 2 ] + , in which the Tl+ ion is coordinated sandwichlike by the eight oxygen atoms of the two crown ether molecules. The lone pair at the thallium ion shows steric activity. [Pb(15-crown-5) 2 ][SbCl 6 ] 2 ·[SbCl 3 (15-crown-5)] (2): Space group Pna2(1), Z = 4, 4631 observed unique reflections, R = 0.048. Lattice dimensions at -70°C: a = 2972.5(3), b = 1481.9(5), c = 1305.5(1) pm. 2 consists of [Pb(15-crown-5)2] 2+ ions, in which the lead ion is coordinated sandwich-like by the ten oxygen atoms of the two crown ether molecules without steric activity of the lone pair of Pb 2+ , of SbCl 6 - ions, and of molecules [SbCl 3 (15-crown-5)], which are already known. [In(12-crown-4) 2 ][SbCl 6 ] 3 ·3CH 3 CN (3): Space group P1̅, Z = 2, 5530 observed unique reflections, R = 0.059. Lattice dimensions at -70°C: a = 1041.8(8), b = 1052(1), c = 1543(2) pm, α = 103.62(9)°, β=108.68(8)°, γ = 99.48(8)°. 3 consists of [In(12-crown-4) 2 ] 3+ ions, SbCl 6 - anions, and crystal CH 3 CN molecules. The In 3+ ion is coordinated sandwich-like by the eight oxygen atoms of the two crown ether molecules, which are disordered in two positions