The ionic crown ether complexes [Tl(12-crown-4)2][SbCl6] (1) and [In(12-crown-4)2][SbCl6]3·3 CH3CN (3) have been prepared by reaction of T1C1 and InCl3, respectively, with SbCl5 in the presence of 12-crown-4 in acetonitrile solution. The lead complex [Pb(15-crown-5)2][SbCl6]2· [SbCl3(15-crown-5)] (2) has been obtained from the reaction of Pb(CH3)2Cl2 with SbCl5 in the presence of 15-crown-5 in acetonitrile solution. 1-3 were characterized by crystal structure determinations.
[Tl(12-crown-4)2][SbCl6] (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][SbCl6]2·[SbCl3(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 Pb2+, of SbCl6- ions, and of molecules [SbCl3(15-crown-5)], which are already known.
[In(12-crown-4)2][SbCl6]3·3CH3CN (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, SbCl6- anions, and crystal CH3CN molecules. The In3+ ion is coordinated sandwich-like by the eight oxygen atoms of the two crown ether molecules, which are disordered in two positions
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