Bis(N-{bis­[meth­yl(phen­yl)amino]phos­phor­yl}-2,2,2-trichloro­acetamide)di­nitrato­dioxidouranium(VI)

In the title compound, [UO2 L 2(NO3)2] {L = N-{bis­[meth­yl(phen­yl)amino]phosphor­yl}-2,2,2-trichloro­acetamide, C16H17Cl3N3O2P}, the UVI ions are eight-coordinated by axial oxido ligands and six equatorial O atoms from the phosphoryl and nitrate groups in a distorted hexa­gonal–bipyramidal geometry. There are disordered fragments in the two coordinating L ligands: the trichloro­methyl group is rotationally disordered between two orientations [occupancy ratio 0.567 (15):0.433 (15)] in one ligand, and a meth­yl(phen­yl)amine fragment is disordered over two conformations [occupancy ratio 0.60 (4):0.40 (4)] in the other ligand. In the crystal structure, intra­molecular N—H⋯O hydrogen bonds between the amine and nitrate groups are observed

Bis{N-[bis­(pyrrolidin-1-yl)phosphor­yl]-2,2,2-trichloro­acetamide}di­nitrato­dioxidouranium(VI)

The crystal structure of the title compound, [U(NO3)2O2(C10H17Cl3N3O2P)2], is composed of centrosymmetric [UO2(L)2(NO3)2] mol­ecules {L is N-[bis­(pyrrolidin-1-yl)phosphor­yl]-2,2,2-trichloro­acetamide, C10H17Cl3N3O2P}. The UVI ion, located on an inversion center, is eight-coordinated with axial oxido ligands and six equatorial oxygen atoms of the phosphoryl and nitrate groups in a slightly distorted hexa­gonal-bipyramidal geometry. One of the pyrrolidine fragments in the ligand is disordered over two conformation (occupancy ratio 0.58:0.42). Intra­molecular N—H⋯O hydrogen bonds between the amine and nitrate groups are found

catena-Poly[neodymium(III)-bis­[μ-N-(dimorpholinophosphor­yl)benzene­sulfonamidato]-sodium(I)-bis­[μ-N-(dimorpholinophosphor­yl)benzene­sulfonamidato]]

The cubic crystal structure of the title compound, [NaNd(C14H21N3O5PS)4]n, is composed of one-dimensional polymeric chains propagating in [100], built up from [Nd(C14H21N3O5PS)4]− anions and sodium cations functioning as linkers. In the complex anion, the Nd3+ ion has an eightfold coordination environment formed by the sulfonyl and phosphoryl O atoms of four bidentate chelating N-(dimorpholinophosphor­yl)benzene­sulfonamidate ligands: the resulting NdO8 polyhedron can be described as inter­mediate between dodeca­hedral and square anti­prismatic. The sodium ion adopts an NaO4 tetra­hedral geometry arising from four monodentate benzene­sulfonamidate ligands. The resulting crystal structure is unusual because it contains substantial voids (800 Å3 per unit cell), within which there is no evidence of included solvent

catena-Poly[sodium-di-μ-aqua-sodium-bis[μ-2,2,2-trichloro-N-(dimorpholinophosphoryl)acetamide]]

The title compound, [Na2(C10H16Cl3N3O4P)2(H2O)2]n, can be considered as a two-dimensional coordination polymer in which one-dimensional chains are connected to each other by inter­molecular C—H⋯O hydrogen bonds involving the water mol­ecules. The NaI ion is five-coordinated in a distorted trigonal-bipyramidal geometry. The connection between the two NaI ions is facilitated by the two μ-O atoms of the carbonyl group of the 2,2,2-trichloro-N-(dimorpholino­phosphor­yl)acetamide (CAPh) ligand. A bridging coordination of the CAPh ligand via the carbonyl O atom is observed for the first time. The bridging water mol­ecules form inter­molecular O—H⋯O hydrogen bonds with the O atoms of the morpholine rings and the phosphoryl groups of neighboring CAPh mol­ecules

How minor structural changes generate major consequences in photophysical properties of RE coordination compounds; resonance effect, LMCT state

Lanthanide coordination compounds of the formula Na[Ln(L)4] (1Ln), where Ln ¼ La3þ, Eu3þ, Gd3þ, Tb3þ, L ¼ [L] and HL ¼ dimethyl(4-methylphenylsulfonyl)amidophosphate, were synthesized. Their structural and spectroscopic properties were discussed in detail based on X-ray diffraction measurements, IR spectroscopy, absorption and emission spectroscopy at 293 and 77 K and theoretical calculations of the intramolecular energy transfer (IET) rates. DFT calculations were used to investigate the 1Ln electronic properties required to calculate the transition rates. 30 and 22 pathways of intramolecular nonradiative energy transfer were examined in the case of 1Eu and 1Tb, respectively. It is shown that the main pathway for sensitization of the lanthanide emission is either the triplet (1Eu) or singlet (1Tb) transfer, occurring mainly through the exchange mechanism. The energy rates for energy transfer from S1 and T1 equal WS ¼ 1:53 105 s 1 (1Eu), WT ¼ 5:14 106 s 1 (1Eu) and WS ¼ 4:09 107 s 1 (1Tb), WT ¼ 6:88 105 s 1 (1Tb). The crucial role of the 7F5 level in the energy transfer process of 1Tb and the participation of the LMCTstate in the depopulation of the ligand singlet state of 1Eu were demonstrated. The influence of the resonance effect on the splitting of the 7F1 level in 1Eu was analyzed. By comparing the properties of 1Ln with the properties of 2Ln coordination compounds, sharing the same ligand and crystallizing in the same crystallographic system (monoclinic), but with a different space group, it is demonstrated how slight structural changes can affect the photophysical properties of Ln compounds.publishe

Tris{N-[bis(pyrrolidin-1-yl)phosphoryl]-2,2,2-trichloroacetamide}trichloridoerbium(III)

The asymmetric unit of the title compound, [ErCl3(C10H17Cl3N3O2P)3], contains two independent molecules. In each molecule, the ErIII ion is six-coordinated in a slightly distorted octahedral ErO3Cl3 geometry with a fac-arrangement of the donor atoms. Intramolecular N—H...Cl hydrogen bonds influence the molecular conformations. Some of the pyrrolidine fragments in the N-[bis(pyrrolidin-1-yl)phosphoryl]-2,2,2-trichloroacetamide ligands are disordered over two conformations of equal occupancy. The unusually porous crystal packing exhibits voids of 162, 158 and 13 Å3 and short intermolecular Cl...O contacts of 2.876 (3) and 3.022 (4) Å

N-{Bis[methyl(phenyl)amino]phosphoryl}-2,2,2-trichloroacetamide

In the asymmetric unit of the crystal structure of the title compound, C16H17Cl3N3O2P, there are two crystallographically independent molecules, which form dimers via N—H...O hydrogen bonding between the N—H group and the P=O group. In the molecular structure, the phosphoryl group is anti to the carbonyl group. The two benzene rings are oriented at dihedral angles of 54.3 (2) and 49.7 (2)° in the two independent molecules

Tris[dimethyl (benzoylamido)phosphato-κ2O,O′](1,10-phenanthroline-κ2N,N′)neodymium(III)

In both independent molecules of the title compound, [Nd(C9H11NO4P)3(C12H8N2)], the NdIII atom is coordinated by six O atoms belonging to three phosphoryl ligands and two N atoms of 1,10-phenanthroline in a dodecahedral geometry. In the phosphoryl ligands, the benzene rings are twisted with respect to the planes of the sp2-hybridized C atoms of the chelate rings by 12.1 (1)–24.7 (1)°

Crystal structure of {μ-6,6′-dimethoxy-2,2′-[ethane-1,2-diylbis(nitrilomethanylylidene)]diphenolato}(methanol)(nitrato)nickel(II)sodium

In the molecular structure of the title compound, [NaNi(C18H18N2O4)(NO3)(CH3OH)], the Ni2+ ion has a slightly distorted square-planar coordination environment defined by two N and two O atoms which belong to a Schiff base ligand, viz. 6,6′-dimethoxy-2,2′-[ethane-1,2-diylbis(nitrilomethanylylidene)]diphenolate. Seven O atoms form the coordination environment of the Na+ ion: four from the Schiff base ligand, two from a bidentate chelating nitrate anion and one O atom from a coordinating methanol molecule. In the crystal, the bimetallic complexes are assembled into chains along the b-axis direction via weak C—H...O hydrogen-bond interactions. Neighbouring chains are in turn connected through bifurcated O—H...O hydrogen bonds that involve the coordinating methanol molecules and the nitrate anions, and through π–π stacking interactions between phenyl rings of neighbouring molecules