Abstract
N-(Trichlorogermyl)trimethylphosphinimine crystallizes in the triclinic space group P1̅ with a = 12.49(2), b = 12.54(3), c = 6.66(1) Å,a = 100.96(10),β = 91.45(14), γ = 102.77(15)°. The structure was solved by Patterson and difference syntheses and refined to R = 0.063 for 2867 independent reflections. In the unit cell there are two symmetry related monomers containing tetracoordinated Ge and one crystallographically centrosymmetric dimer with a planar four-membered [GeN]2 ring exhibiting trigonal-bipyramidal pentacoordinated Ge and trigonal N. Significant differences are observed in the bond lengths from pentacoordinated Ge to its equatorial and axial ligands: Ge-Neq 1.837(7), Ge-Nax 1.972(7), Ge-Cleq 2.176(2) and 2.170(2), Ge-Clax 2.345(3) Å. The Ge-Neq distance is similar to that observed in tetracoordinated derivatives [1.81-1.87 Å], whereas the Ge-Nax distance is 0.22 Å shorter than that observed for the axial N→Ge coordinate bond in hitherto known pentacoordinated derivatives [2.19-2.24 Å]. The very short Ge-N bond length of 1.737(8) Å in the monomer which is 0.07 Å shorter than in other tetracoordinated derivatives may be indicative of the involvement of a (p→d)π component.

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