Crystal structure of (1,10-phenanthroline-κ~2N,N')- dimethyl-formamidepentaaqua-thulium(III) trichloride monohydrate, [Tm(C _(12)H_8N_2)((CH_3)_2NCHO) (H_2O)_5]Cl_3·H_2O, C _(15)H_(27)Cl_3N_3O_7Tm

摘要

(Equation presentation) (Table presentation) Source of material A mixture of TmCl3.6H2O (0.0804 g, 0.21 mmol) and phenanthroline (phen, 0.0398 g, 0.20 mmol) was dissolved in 10 ml acetonitrile, then L ligand (methylenediphosphonate, 0.20mmol) and DMF (N,N-dimethylformamide, 3 drops) were added under stirring at room temperature. The clear colourless solution was stirred for 6.5 hours at room temperature. The insoluble residues were removed by filtration, and the filtrate was allowed to be evaporated slowly at room temperature for two weeks to yield colourless crystals. Discussion Lanthanide complexes have attracted attention due to their potential applications in fluorescence materials, electroluminescent devices, bioassays, luminescent probes, catalytic and ion exchange fields [1, 2]. Phosphoryl(methylenediphosphonate) has been confirmed to be a very efficient ligand, it can form stable complexes with lanthanide ions. In recent years, many lanthanide complexes containing methylenediphosphonate (L), such as [Nd(OTf)2(L)2(OH)2](OTf), [La(L)4](OTf)3(CH3CN)3, [Ln(NO_3)3(L)2](CH3CN)2, were reported [3]. Phenanthroline is a very valid bidentate ligand, so it was chosen as an auxiliary ligand to form mixed-ligand lanthanide complexes, such as [CeCl3(phen)2DMF].DMF [4]. Since the lanthanide cations are very oxophilic, they are expected to interact strongly with highly polarized oxygen-bearing functional groups.We are interested in the reactions of lanthanide chloride with phosphoryl and phen, becauce it can always produce diverse compounds. In our previous work, some lanthanide complexes with (L) or phen have been synthesized and structurally characterized, such as [CeCl3(phen)2DMF].DMF [4] and [Ce(NO_3)3(L)2] [5]. In this paper, we report a complex [Tm(phen)(DMF)(H2O)5]Cl3. H2O which is obtained by the similar reaction. Single-crystal X-ray diffraction study revealed that the mononuclear complex [Tm(phen)(DMF)(H2O)5]Cl3.H2O was obtained despite the presence of tetrakis(O-isopropyl)methylenediphosphonate. The presence of methylenediphosphonate may have subtle effects on the coordination of phen ligand with lanthanide atom, just as in our previous work [4]. In the title complex, the phen, water and even the solvent DMF molecules are coordinated to the central Tm atom. The phenomenon that the DMF molecule was coordinated to the lanthanide atom through the oxygen atom also happened in preparing the complex ([CeCl3(phen)2DMF].DMF [4]). The thulium atom is coordinated by two nitrogen atoms from one phen ligand, one oxygen atom fromDMF, and five oxygen atoms from five water molecules with the total coordination number of 8. There are also three chloride ions and one freewater molecule out of the coordination sphere. The average Tm-N(phen) bond distance of 2.489 ? is shorter than the average Tm-N(phen) bond distance of 2.536 ? in the complex [Tm2(phen)4(H2O)2(OH)2]-.(phen)2(NO_3)4 [6]. The Tm-O(DMF) bond distance is 2.249 ?, which is larger than Tm-O(DMF) bond distance of 2.332?in the complex [Tm(DMF)4(H2O)3(μ-CN)Fe(CN)5].1.25H2O [7]. The ions and molecules of the title structure form a two-dimensional network through the hydrogen bonds O-H...Cl and O-H...O. The hydrogen bonds O-H...Cl are formed between O-H donors of water molecules and chloride ions (O...Cl = 3.029-3.204 ?, O-H...Cl = 173.19-176.91°); while the hydrogen bond O2-H2...O7 is formed between O2-H2 group of the coordinated water molecule and O7 atom of the free water molecule (O2...O7 = 2.637 ?, O2-H2D...O7 = 175.75°). (Table presentation).