CRYSTALCHEMICAL ANALYSIS OF THE STEREOCHEMISTRY OF THE CATIONS AND ANIONS IN BIS(TRIPHENYLPHOSPHINE)IMINIUM DI(PHTHALOCYANINATO)METALATES OF THE RARE-EARTH ELEMENTS, (PNP)[LN(PC(2-))(2)]CENTER-DOT-XH2O (LN=LA,GD, TM, X-LESS-THAN-OR-EQUAL-TO-0.5)

Of the isostructural series of monoclinic (PNP)[Ln(Pc)(2)].xH(2)O comp ounds (Ln = La...Tm) the crystal structures of the complex salts of te rvalent La (1), Gd (2) and Tm (3) have been determined by single cryst al X-ray diffraction analysis. Unit cell data for 2: space group P2(1) /c; a = 15.172(8), b = 20.826(2), c = 25.876(3) Angstrom, beta = 95.19 (3)degrees, V = 8143(4)Angstrom(3), Z = 4; 1 and 3 are isostructural w ith 2. The lanthanide ion occupies the center of a nearly ideal square antiprism, although the two staggered phthalocyanine rings are severe ly distorted in an unsymmetrical funnel-shaped fashion due to electron ic, steric, and packing influences in the crystal lattice. Steric effe cts dictate also the geometry of the PNP cation, which adopts a hybrid conformation whose structural characteristics are between the common linear and bent conformers with medium short P-N distances (1.562 Angs trom) and large P-N-P angles in the range 165.6 degrees (1) > 158.3 de grees (2) > 156.1 degrees (3). The strong IR bands at ca. 1375 cm assi gned to the asym. (P-N) stretch are diagnostic for this hybrid conform ation, The presence of water of crystallization in the periphery of th e diphthalocyanine anion is confirmed. The shortest contact distance i s observed to one of the bridging nitrogen atoms of the Pc(2-) ligand (3.02 Angstrom) indicating a weak(HO-H...N)hydrogen bond.