Triphenylphosphine oxide (L) as solvent and ligand for metallophthalocyaninates; Synthesis and structure of [{Li(L)}(2)(mu-pc)], [Li(L)(4)][Lipc] center dot solvate, [Mg(L)pc] center dot solvate, and [Zn(L)pc] center dot solvate

Triphenylphosphine oxide (L) coordinates to metallophthalocyaninates of Li, Mg and Zn at 300 degrees C. After purification and recrystallization in di fferent solvents the very soluble and stable title compounds have been isol ated and structurally characterized. In [{Li(L)}(2)(mu-pc)], the Li atom li es in a distorted tetragonal pyramid of four isoindole N atoms (N-i) at a d istance varying between 2.163(5) and 2.301(5) Angstrom, and an O atom at 1. 863(5) Angstrom. In [Li(L)(4)] . [Lipc] . S, the Li atom of the cation coor dinates four O atoms in a distorted tetrahedral arrangement at a distance v arying from 1.887(9) to 1.953(9) Angstrom, while the Li atom of the anion i s in a quasi quadratic planar geometry of four Ni atoms (1.951(9)-1.977(9) Angstrom) with the Li atom being displaced by 0.15 Angstrom out of the (N-i )(4) plane. The structural data of the distorted tetragonal pyramidale Mg(N -i)(4)O moiety in [Mg(L)pc] and the solvates [Mg(L)pc] . S (S = CH2Cl2, thf , 2py) generally do not vary significantly: Mg-N-i/2.035(3) -2.061(3) Angst rom, Mg-O/1.955(2)-2.000(3) Angstrom. The Mg atom is displaced by ca. 0.52 Angstrom out of the (N-i)(4) plane towards the O atom and the Mg-O-P moiety is bent (ca, 153 degrees). [Zn(L)pc] . S crystallizes as a mixed crystal o f equal parts of the conformer with a bent (155.1(3)degrees) and that of a quasi linear Zn-O-P moiety (174.2(3)degrees). Structural data of the Zn(N-i )(4)O moiety: (Zn-N-i)(av): 2.024/2.013 Angstrom; Zn-O: 2.050(4)/2.081(4) A ngstrom; Zn-(N-i)(4): 0.40/0.33 Angstrom. In the crystal, the Mg and Zn der ivates aggregate in double layers forming pairs. The pc ligands in the tric linic complexes with good overlap of the neighbouring pc ligands are in a w aving conformation, while those in the monoclinic complexes with weak overl ap are in a concave conformation.