Crystal structure of trichloro-bis(N,N′-1,10-phenanthroline) - dimethylformamide-cerium(III) dimethylformamide solvate, Ce(C12H8N2)2((CH3)2NCHO)Cl3 · (CH3)2NCHO

Abstract

Source of material PrO) 2 )] (0.1033 g, 0.3 mmol) was dissolved in 10 ml methylene dichloride. The solution yielded white precipitation immediately when phen (1,10-phenanthroline, 0.1189 g, 0.6 mmol) was added after the solution was stirred for 6 h at RT. Then the suspension was stirred for another 6 h. After filtration, the filtrate was allowed to stand still. Slow evaporation of the solvent yielded yellow powder solid. Recrystallization of the solid from DMF (N,N-dimethylformamide) gave yellow crystals. DiscussionLanthanide complexes have interesting photophysical properties, and the chemistry of metal phosphonates has been a research field of rapid expansion due to their potential application in the area of catalysis, ion exchange and material chemistry. Phen (phenanthroline), usually acting as a bidentate co-ligand, is mostly used as an auxiliary ligand in the mixed-ligand complexes to enhance the fluorescent properties and control the dimensionality. We are interested in lanthanoid methylenediphosphonate complexes [1]. The single-crystal X-ray diffraction study revealed that the mononuclear complex CeCl 3 (phen) 2 DMF · DMF was obtained despite the presence of tetrakis(O-isopropyl)methylenediphosphonate (figure, top). In the title complex, phen just acts as the second ligand. The IR spectrum also illustrates only phen coordinated to the central atom besides the chloride ions and DMF. This shows that the coordination ability of CH 2 [P(O)( i PrO) 2 ] 2 is weaker than that of phen. Most surprisingly, the DMF which we used as solvent is coordinated to the Ce atom through the oxygen atom. In the complex [Nd 4 (OH){(p-tert-butyltetrathiacalix[4]arene-4H)-(DMF)} 2(DMF)6(DMSO)2](NO3)3 · 3H2O [2], both DMF and DMSO solvate are also found as ligands of the rare earth atom. The cerium atom is coordinated by four nitrogen atoms from two phen ligands, one oxygen atom from DMF, and three chloride ions with the total coordination number of 8. There is also a free DMF molecule out of the coordination sphere. The average CeN bond distance of 2.699 Å is slightly shorter than the average value of 2.713 Å for the complex [Ce 2(IDA)2(C2O4) (phen) figure (figure, bottom) shows that the title compound is a supermolecular assembly formed by the p-p packing interaction of phen ligands along two perpendicular directions.

Crystal structure of bis(O,O'-tetraisopropylmethylenediphosphonate)- cerium(III) trinitrate, Ce(NO3)3[CH2P2O2(C3H7O)4]2

“…In our previous work, some lanthanide complexes with tetraisopropylmethylenediphosphonate (L) and bis(diphenylphosphino)methane dioxide (dppmo 2 )h ave been synthesized and structurally characterized [7][8][9][10]. When we attemp to synthesize Ce(NO 3 ) 2 Cl complex of tetraisopropylmethylenediphosphonate, an unexpected title compound was obtained as aproduct.…”