Crystal structure of tetra-phenyl phosphate tetra-kis-[dimethyl (2,2,2-tri-chloro-acet-yl)phos-pho-ramidato]lutetium(III), PPh4[LuL4].

A lutetium(III) complex based on the anion of the ligand dimethyl (2,2,2-tri-chloro-acet-yl)phospho-ramidate (HL) and tetra-phenylphosphonium, of composition PPh4[LuL 4] (L = CAPh = carbacyl-amido-phosphate), or (C24H20)[Lu(C4H6Cl3NO4P)4], has been synthesized and structurally characterized. The X-ray diffraction study of the compound revealed that the lutetium ion is surrounded by four bis-chelating CAPh ligands, forming the complex anion [LuL 4]- with a coordination number of 8[O] for LuIII, while PPh4 + serves as a counter-ion. The coordination geometry around the Lu3+ ion was determined to be a nearly perfect triangular dodeca-hedron. The complex crystallizes in the monoclinic crystal system, space group P21/c, with four mol-ecules in the unit cell. Weak hydrogen bonds O⋯HC(Ph), Cl⋯HC(Ph) and N⋯HC(Ph) are formed between the cations and anions. For a comparative study, HL-based structures were retrieved from the Cambridge Structural Database (CSD) and their geometries and conformations are discussed. A Hirshfeld surface analysis was also performed.

Lanthanide mixed-ligand complexes of the [Ln(CAPh)3(Phen)] and [LaxEu1-x(CAPh)3(Phen)] (CAPh = carbacylamidophosphate) type. A comparative study of their spectral properties.

A series of complexes Ln(Pip)3(Phen) (Ln(iii) = La, Ce-Nd, Sm-Lu, Y; HPip (CAPh type ligand) = 2,2,2-trichloro-N-(dipiperidin-1-yl-phosphoryl)acetamide, Phen = 1,10-phenanthroline) has been synthesized. The lanthanum(iii) doped europium(iii) complexes ([LaxEu1-x(Pip)3(Phen)], x = 0.99, 0.95, 0.50) have been obtained by the co-crystallization method. The complexes have been characterized by means of X-ray diffraction, IR, (1)H and (31)P-NMR and absorption spectroscopy. Emission and excitation luminescence spectra were recorded at 295 and 77 K. The lifetime values (τ) for the emission of all europium complexes were determined. The (5)D0 luminescence quantum efficiency is 73-89%. The symmetries of the nearest europium surrounding in pure and doped complexes were evaluated from the Stark splitting of (5)D0-(7)FJ transitions. Crystal structures of [Ln(Pip)3(Phen)] (Ln = Nd (1), Eu (2) and Tb (3)) have been determined. Lattice parameters of the [Ln(Pip)3(Phen)] (Ln = Tb, Yb) and the doped [LaxEu1-x(Pip)3(Phen)] (x = 0.99, 0.95, 0.50) complexes have been measured. The presence of four polymorphs within a number of rare earth elements has been estimated: two in triclinic (Ln1 = La, Nd; Ln2 = Eu), one in the monoclinic (Ln3 = Tb) and one in the rhombic (Ln4 = Tb, Yb) symmetry. Complex 3 can be obtained in two crystal modifications: monoclinic and orthorhombic ones.

N-[Bis(benzylamino)phosphoryl]-2,2,2-trichloroacetamide.

In the title compound, C(16)H(17)Cl(3)N(3)O(2)P, the P atom has a slightly distorted tetra-hedral configuration. The conformations of the carbonyl and phosphoryl groups are anti to each other. In the crystal, inter-molecular N-H⋯O hydrogen bonds link the mol-ecules into infinite chains parallel to the b axis.

Bis(N-{bis-[meth-yl(phen-yl)amino]phos-phor-yl}-2,2,2-trichloro-acetamide)di-nitrato-dioxidouranium(VI).

In the title compound, [UO(2)L(2)(NO(3))(2)] {L = N-{bis-[meth-yl(phen-yl)amino]phosphor-yl}-2,2,2-trichloro-acetamide, C(16)H(17)Cl(3)N(3)O(2)P}, the U(VI) ions are eight-coordinated by axial oxido ligands and six equatorial O atoms from the phosphoryl and nitrate groups in a distorted hexa-gonal-bipyramidal geometry. There are disordered fragments in the two coordinating L ligands: the trichloro-methyl group is rotationally disordered between two orientations [occupancy ratio 0.567 (15):0.433 (15)] in one ligand, and a meth-yl(phen-yl)amine fragment is disordered over two conformations [occupancy ratio 0.60 (4):0.40 (4)] in the other ligand. In the crystal structure, intra-molecular N-H⋯O hydrogen bonds between the amine and nitrate groups are observed.

Bis{N-[bis-(pyrrolidin-1-yl)phosphor-yl]-2,2,2-trichloro-acetamide}di-nitrato-dioxidouranium(VI).

The crystal structure of the title compound, [U(NO(3))(2)O(2)(C(10)H(17)Cl(3)N(3)O(2)P)(2)], is composed of centrosymmetric [UO(2)(L)(2)(NO(3))(2)] mol-ecules {L is N-[bis-(pyrrolidin-1-yl)phosphor-yl]-2,2,2-trichloro-acetamide, C(10)H(17)Cl(3)N(3)O(2)P}. The U(VI) 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 hexa-gonal-bipyramidal geometry. One of the pyrrolidine fragments in the ligand is disordered over two conformation (occupancy ratio 0.58:0.42). Intra-molecular N-H⋯O hydrogen bonds between the amine and nitrate groups are found.

catena-Poly[neodymium(III)-bis-[µ-N-(dimorpholinophosphor-yl)benzene-sulfonamidato]-sodium(I)-bis-[µ-N-(dimorpholinophosphor-yl)benzene-sulfonamidato]].

The cubic crystal structure of the title compound, [NaNd(C(14)H(21)N(3)O(5)PS)(4)](n), is composed of one-dimensional polymeric chains propagating in [100], built up from [Nd(C(14)H(21)N(3)O(5)PS)(4)](-) anions and sodium cations functioning as linkers. In the complex anion, the Nd(3+) ion has an eightfold coordination environment formed by the sulfonyl and phosphoryl O atoms of four bidentate chelating N-(dimorpholinophosphor-yl)benzene-sulfonamidate ligands: the resulting NdO(8) polyhedron can be described as inter-mediate between dodeca-hedral and square anti-prismatic. The sodium ion adopts an NaO(4) tetra-hedral geometry arising from four monodentate benzene-sulfonamidate ligands. The resulting crystal structure is unusual because it contains substantial voids (800 Å(3) 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, [Na(2)(C(10)H(16)Cl(3)N(3)O(4)P)(2)(H(2)O)(2)](n), can be considered as a two-dimensional coordination polymer in which one-dimensional chains are connected to each other by inter-molecular C-H⋯O hydrogen bonds involving the water mol-ecules. The Na(I) ion is five-coordinated in a distorted trigonal-bipyramidal geometry. The connection between the two Na(I) ions is facilitated by the two µ-O atoms of the carbonyl group of the 2,2,2-trichloro-N-(dimorpholino-phosphor-yl)acetamide (CAPh) ligand. A bridging coordination of the CAPh ligand via the carbonyl O atom is observed for the first time. The bridging water mol-ecules form inter-molecular O-H⋯O hydrogen bonds with the O atoms of the morpholine rings and the phosphoryl groups of neighboring CAPh mol-ecules.

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

The asymmetric unit of the title compound, [ErCl(3)(C(10)H(17)Cl(3)N(3)O(2)P)(3)], contains two independent mol-ecules. In each mol-ecule, the Er(III) ion is six-coordinated in a slightly distorted octa-hedral ErO(3)Cl(3) geometry with a fac-arrangement of the donor atoms. Intra-molecular N-H⋯Cl hydrogen bonds influence the mol-ecular 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 Å(3 )and short inter-molecular Cl⋯O contacts of 2.876 (3) and 3.022 (4) Å.

N-{Bis[meth-yl(phen-yl)amino]phosphor-yl}-2,2,2-trichloro-acetamide.

In the asymmetric unit of the crystal structure of the title compound, C(16)H(17)Cl(3)N(3)O(2)P, there are two crystallograph-ically independent mol-ecules, which form dimers via N-H⋯O hydrogen bonding between the N-H group and the P=O group. In the mol-ecular 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 mol-ecules.