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.

Crystal structure of the sodium salt of mesotrione: a triketone herbicide.

The crystal structure of the sodium salt of mesotrione, namely, catena-poly[[sodium-µ3-2-[(4-methane-sulfonyl-2-nitro-phen-yl)carbon-yl]-3-oxo-cyclo-hex-1-en-1-olato] ethanol monosolvate], {[Na(C14H12NO7S)]C2H5OH}n, is described. The X-ray structural analysis results reveal that the coordination sphere is established by two chelating O atoms, the O atom of the coordinated ethanol mol-ecule, and an O atom from the methyl-sulfonyl group of a neighboring mol-ecule. Simultaneously, an O atom of the cyclo-hexane fragment serves as a bridge to a neighboring sodium ion, forming a flat Na-O-Na-O quadrangle, thereby forming a mono-periodic polymer. The structure displays O-H⋯O hydrogen bonds and C-H⋯O short contacts. Thermogravimetric analysis (TGA) data indicate that the sodium salt of mesotrione decomposes in four stages.

Lanthanide complexes based on a new bis-chelating carbacylamidophosphate (CAPh) scorpionate-like ligand.

The novel bis-chelating carbacylamidophosphate type ligand, tetramethyl[pyridine-2,6-diyldi(iminocarbonyl)]diamidophosphate (H2L), and its sodium salt, NaHL, have been synthesized and their structural properties have been investigated. Coordination compounds of lanthanides [Ln(HL)2NO3]·i-PrOH (Ln = Eu3+, Tb3+) were obtained for the first time, isolated in the individual state and characterized by means of IR and NMR spectroscopies, electrospray ionization mass spectrometry (ESI-MS), potentiometric titration, and elemental, thermal gravimetric and X-ray diffraction analyses. It was shown that H2L behaves like a scorpionate type ligand and in a mono-deprotonated form coordinates in a tridentate manner via the oxygen atoms of phosphoryl and carbonyl groups with formation of a mononuclear metal complex. The protonation constants of H2L and stability constants of Eu3+ and Tb3+ complexes have been determined. According to the results of X-ray diffraction analysis the H2L and [Ln(HL)2NO3]·i-PrOH molecules have monomeric structure but NaHL is a dimer. The Hirshfeld surface and fingerprint plots of the compounds have been used to analyze various hydrogen bonds and intermolecular interactions displayed in the crystal structure.

Pharmacophores Modeling in Terms of Prediction of Theoretical Physicochemical Properties and Verification by EXPERIMENTAL correlations of Carbacylamidophosphates (CAPh) and Sulfanylamidophosphates (SAPh) Tested as New Carbonic Anhydrase Inhibitors.

BACKGROUND: The function of Carbonic anhydrase is to facilitate the physiological process i.e. interconversion of CO2 to HCO3 - by hydration. Carbonic anhydrase enzyme plays a vital role in different physiological processes to regulate pH as well as regulate the inner environment of CO2 and secretion of electrolytes. METHODS: Six representatives of amidophosphate derivatives (L1-L6) were synthesized and evaluated for their biological activities against carbonic anhydrase enzyme. RESULTS: Out of six derivatives, L1 (IC50 = 12.5 ± 1.35 µM), and L2 (IC50 = 3.12 ± 0.45 µM) showed potent activity against BCA-II. While (L3, L4 and L5) showed weak inhibitory activity with IC50 values of 24.5 ± 2.25, 55.5± 1.60, and 75.5 ± 1.25 µM, respectively and were found to be weak inhibitors of carbonic anhydrase as compared to acetazolamide (IC50 =0.12± 0.03µM), used as standard inhibitor. A computational Petra/Osiris/Molinspiration/DFT (POM/DFT) based model has been expanded for the determination of physicochemical parameters governing the bioactivity amidophosphate derivatives (L1-L6) containing (O1 --- O2) pharmacophore site. The six compounds (L1-L6) analyzed here were previously experimentally and now virtually screened for their anti-carbonic anhydrase activity. CONCLUSION: The highest anti-carbonic anhydrase activity was obtained for compound L2, which exhibited excellent bioactivity (% of inhibition = 95%), comparable to acetazolamide (% of inhibition = 89%). The compound L3 represents increased activity as compared to its analogues (L4-L6). The increase of bioactivity from L3 to L4-L6 could be attributed to the presence of a minimum of steric effect of substituents of P=O moiety which plays a decisive template part in the organization of anti-carbonic anhydrase (O1---O2) phramacophore site. Moreover, it is inexpensive, has little side effects and possible inclusions in selective anti-carbonic anhydrase agents design.

Crystal structure of aqua-tris-{µ-N-[bis(diethyl-amino)phosphoryl]-2,2,2-tri-chloroacetamidato-κ3O,O':O}calciumsodium.

In the mol-ecular structure of the title compound, [CaNa(C10H20Cl3N3O2P)3(H2O)], the Ca2+ ion has a slightly distorted octa-hedral coordination environment defined by six O atoms which belong to the carbonyl and phosphoryl groups of the three coordinating ligands. Two Cl atoms of CCl3 groups and four O atoms form the coordination environment of the Na+ ion: three from the carbonyl groups of ligands and one O atom from a coordinating water mol-ecule. In the crystal, the bimetallic complexes are assembled into chains along the c-axis direction via O-H⋯O hydrogen bonds that involve the coordinating water mol-ecules and the phosphoryl groups.

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.

Hexa-µ2-chlorido-µ4-oxido-tetra-kis[(morpholine-κN)copper(II)] methanol disolvate.

In the title solvate, [Cu4(µ2-Cl)6(µ4-O)(C4H9NO)4]·2CH3OH, each Cu(2+) ion in the tetra-nuclear complex has a trigonal-bipyramidal coordination arising from three bridging chloride ions in equatorial positions and the central µ4-O(2-) ion and morpholine N atom in axial positions. The morpholine rings adopt chair conformations, with the N-Cu bonds in equatorial orientations. In the crystal, the components are linked by N-H⋯O and O-H⋯O and O-H⋯Cl hydrogen bonds, which generate a three-dimensional network. One methanol mol-ecule is disordered over two sets of sites in a 0.642 (9):0.358 (9) ratio.

Methyl N-(di-meth-oxy-phosphor-yl)carbamate.

In the title compound, CH3OC(O)NHP(O)(OCH3)2, the P atom has a slightly distorted tetra-hedral configuration. The mixed imide moiety can be described as cisoid-transoid in which the two opposing dipoles (P=O and C=O) are oriented with a O=C⋯P=O torsion angle of 150.88(18)°. In the crystal, molecules are linked by pairs of N-H⋯O hydrogen bonds, forming inversion dimers.

Chlorido[N,N'-dibenzyl-N''-(trichloroacetyl)phosphoramidato-κ2O,O'](1,10-phenanthroline-κ2N,N')copper(II).

In the title complex, [Cu(C16H16Cl3N3O2P)Cl(C12H8N2)], the Cu(II) cation presents a square-pyramidal environment, where the CuO2N2 base is formed by two O atoms from carbonyl and phosphoryl groups, and by two N atoms from a 1,10-phenanthroline molecule. A coordinated Cl atom occupies the apex. N-H···Cl hydrogen bonds link the molecules into one-dimensional chains. The trichloromethyl group is rotationally disordered over two positions, with occupancies of 0.747 (7) and 0.253 (7).

N,N'-Dimethyl-N''-(trichloroacet-yl)phospho-ramide.

In the title compound, C4H9Cl3N3O2P or CCl3C(O)NHP(O)(NHCH3)2, the P atom has a strongly distorted tetra-hedral geometry due to the formation of intermolecular strong hydrogen bonds involving the N atoms. In the crystal, N-H⋯O=P and N-H⋯O=C hydrogen bonds connect the mol-ecules into a two-dimensional array parallel to (100). An intra-molecular P⋯O contact [P⋯O = 2.975 (3) Å] is observed. The CCl3 group is rotationally disordered, with occupancies of 0.60 (3) and 0.40 (3).

2-Ureido-1,3-thia-zol-3-ium dihydrogen phosphate.

The title compound, C(4)H(6)N(3)OS(+)·H(2)PO(4) (-), (I), was obtained as a result of hydrolysis of [(1,3-thia-zol-2-yl-amino)-carbon-yl]-phospho-ramidic acid, (II), in water. X-ray analysis has shown that the N-P bond in (II) breaks, leading to the formation of the substituted carbamide (I). This compound exists as an inter-nal salt. The unit cell consists of a urea cation and an anion of H(2)PO(4) (-). Protonation of the N atom of the heterocyclic ring was confirmed by the location of the H atom in a difference Fourier map. The mol-ecules of substituted urea are connected by O⋯O hydrogen bonds into unlimited planes. In turn, those planes are connected to each other via N-H⋯O hydrogen bonds with mol-ecules of phospho-ric acid, forming a three-dimensional polymer.

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.