Relationship between the Skew Angle and Interplanar Distance in Four Bis(phthalocyaninato)lanthanide(III) Tetrabutylammonium Salts ([NBu<i><sup>n</sup></i><sub>4</sub>][Ln<sup>III</sup>Pc<sub>2</sub>]; Ln = Nd, Gd, Ho, Lu)
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Four crystal structures of the title complexes have been analyzed by X-ray crystallography. 1: C80H68N17Nd, a = 17.0545(6) Å, c = 22.807(3) Å, tetragonal, P4/ncc, Z = 4. 2: C80H68N17Gd, a = 17.399(8) Å, c = 11.377(6) Å, tetragonal, P4212, Z = 2. 3: C80H70N17OHo, a = 18.096(5) Å, c = 11.079(6) Å, tetragonal, P4212, Z = 4. 4: C80H70N17OLu, a = 18.171(3) Å, c = 10.987(4) Å, tetragonal, P4/nmm, Z = 2. The [LnIIIPc2]- and [NBun4]+ ions in each crystal stack alternately in a column along the 4-fold axis. The Ln(III) cation of each [LnIIIPc2]- is eight-coordinated by two phthalocyanato dianions (Pc). The interplanar distances between the two Pc rings have a linear relationship to the ionic radii of the central Ln(III) cations. The skew angles between the two Pc rings are 6.2, 34.4, 43.2, and 45.0° for the Nd, Gd, Ho, and Lu complexes, respectively. The skew angle seems to depend on the strength of the π−π interaction between the two Pc rings.
