Non‐Planar Lithium‐Phthalocyanine in the Double Salt ( n Bu 4 N) 2 [Lipc]PF 6

We report the synthesis of the diamagnetic double salt bis(tetra( n ‐butyl)ammonium) phthalocyanato(2‐)lithate hexafluorophosphate ( n Bu 4 N) 2 [Lipc]PF 6 [pc = phthalocyanine, n Bu 4 N + = tetra( n ‐butyl)ammonium] in dme (dme = dimethoxyethane). According to single‐crystal X‐ray diffraction structure analysis [ P $\bar{1}$ , a = 8.642(2) Å, b = 12.820(3) Å, c = 15.019(3) Å, α = 83.01(3)°, β = 87.87(3)°, γ = 74.45(3)°, Z = 1, R 1 = 6.4 %], the phthalocyanine building bloc shows a substantial distortion of the macrocyclic ring from planarity. The deviation from D 4 h symmetry originates from packing effects induced by the two tetra( n ‐butyl)ammonium cations located above and below the macrocycle. DFT structure optimization starting from the experimental non‐planar configuration produces a fully planar complex anion [Lipc] – .