Phosphorane Iminato Complexes of Antimony. The Crystal Structures of [Sb
2Cl
5(NPMe
3)
2][SbCl
6] · CH
3CN and [SbCl(NPPh
3)]
2[SbCl
6]
2 · 6 CH
3CN The title compounds are formed by reaction of antimony pentachloride in acetonitrile solution with the phosphorane iminato complexes SbCl
2(NPMe
3) and SbCl
2(NPPh
3), respectively, which themselves are synthesized by reaction of antimony trichloride with Me
3SiNPR
3 (R = Me, Ph). The complexionic compounds are characterized by
121Sb Mössbauer spectroscopy and by crystal structure determinations. [Sb
2Cl
5(NPMe
3)
2][SbCl
6] · CH
3CN: Space group P4
1, Z = 4, 3 698 observed unique reflections, R = 0.022. Lattice dimensions at ?60°C: a = b = 1 056.0(1), c = 2 709.6(2) pm. The structure consists of SbCl
6? ions and cations [Sb
2Cl
5(NPMe
3)
2(CH
3CN)]
+, in which one Sb
III atom and one Sb
V atom are bridged by the N atoms of the phosphorane iminato ligands. [SbCl(NPPh
3)]
2[SbCl
6]
2 · 6 CH
3CN: Space group P1 , Z = 2, 5 958 observed unique reflections, R = 0.033. Lattice dimensions at ?60°C: a = 989.4(11), b = 1 273(1), c = 1 396(1) pm, α = 78.33(7), β = 77.27(8)°, γ = 86.62(8)°. The structure consists of SbCl
6? ions and centrosymmetric cations [SbCl(NPPh
3)(CH
3CN)
2]
22+, in which the antimony atoms are bridged by the N atoms of the phosphorane iminato ligands.
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