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

A lutetium(III) complex based on the anion of the ligand dimethyl (2,2,2-tri-chloro-acet-yl)phospho-ramidate (H) and tetra-phenylphosphonium, of composition PPh[Lu ] ( = CAPh = carbacyl-amido-phosphate), or (CH)[Lu(CHClNOP)], 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 [Lu ] with a coordination number of 8[O] for Lu, while PPh serves as a counter-ion. The coordination geometry around the Lu ion was determined to be a nearly perfect triangular dodeca-hedron.

Synthesis, crystal structure and Hirshfeld surface analysis of the tetra-kis complex NaNdPyr(-PrOH)·-PrOH with a carbacyl-amido-phosphate of the amide type.

The tetra-kis complex of neodymium(III), tetra-kis-{μ--[bis-(pyrrolidin-1-yl)phos-phor-yl]acet-am-id-ato}bis(pro-pan-2-ol)neodymiumsodium pro-pan-2-ol monosol-vate, [NaNd(CHClNO)(CHO)]·CHO or NaNdPyr(-PrOH)·-PrOH, with the amide type CAPh ligand bis(,-tetra-methylene)(tri-chloro-acetyl)phos-phoric acid tri-amide (HPyr), has been synthesized, crystallized and characterized by X-ray diffraction. The complex does not have the tetra-kis-(CAPh)lanthanide anion, which is typical for ester-type CAPh-based coordin-ation compounds. Instead, the NdO polyhedron is formed by one oxygen atom of a 2-propanol mol-ecule and seven oxygen atoms of CAPh ligands in the title compound.

Crystal structure of bis-{3-(3,4-di-meth-oxy-phen-yl)-5-[6-(pyrazol-1-yl)pyridin-2-yl]-1,2,4-triazol-3-ato}iron(II)-methanol-chloro-form (1/2/2).

The unit cell of the title compound, [Fe(CHNO)]·2CHOH·2CHCl, consists of a charge-neutral complex mol-ecule, two methanol and two chloro-form mol-ecules. In the complex, the two tridentate 2-(5-(3,4-di-meth-oxy-phen-yl)-1,2,4-triazol-3-yl)-6-(pyrazol-1-yl)pyridine ligands coordinate to the central Fe ion through the N atoms of the pyrazole, pyridine and triazole groups, forming a pseudo-octa-hedral coordination sphere. Neighbouring tapered mol-ecules are linked through weak C-H(pz)⋯π(ph) inter-actions into one-dimensional chains, which are joined into two-dimensional layers through weak C-H⋯N/C/O inter-actions.

Eu and Tb coordination compounds with phenyl-containing carbacylamidophosphates: comparison with selected Ln β-diketonates.

Materials based on Eu and Tb coordination compounds are of great interest due to their strong red and green luminescence. Appropriate selection of ligands plays a huge role in optimizing their photophysical properties. Another very helpful instrument for such optimization is theoretical modelling, which permits the prediction of the emissive properties of materials through intramolecular energy transfer analysis.

Order-Disorder, Symmetry Breaking, and Crystallographic Phase Transition in a Series of Bis(-thiocyanate)iron(II) Spin Crossover Complexes Based on Tetradentate Ligands Containing 1,2,3-Triazoles.

We report herein a series of neutral -thiocyanate mononuclear spin crossover (SCO) complexes, [FeL(NCS)] (-), based on tetradentate ligands L obtained by reaction of N-substituted 1,2,3-triazolecarbaldehyde with 1,3-propanediamine or 2,2-dimethyl-1,3-diaminopropane [L = ,-bis((1,5-dimethyl-1-1,2,3-triazol-4-yl)methylene)propane-1,3-diamine/-2,2-dimethylpropane-1,3-diamine, / and ,-bis((1-ethyl/1-propyl-1-1,2,3-triazol-4-yl)methylene)-2,2-dimethylpropane-1,3-diamine, /]. The thermal-induced SCO behavior is characterized by abrupt transitions with an average critical temperature (Δ)/hysteresis loop width (Δ) in the range 190-252/5-14 K, while the photo-generated metastable high-spin (HS) phases are characterized by temperatures in the range 44-59 K. Single crystal analysis shows that except , all compounds experience reversible symmetry breaking coupled with the thermal SCO.

Crystal structure of caesium dimethyl--benzoyl-amido-phosphate monohydrate.

The caesium salt of dimethyl--benzoyl-amido-phosphate, namely, aqua-[di-meth-yl (-benzoyl-amido-κ)phospho-nato-κ]caesium, [Cs(CHNOP)(HO)] or Cs·HO, is reported. The compound crystallizes in the monoclinic crystal system in the 2/ space group and forms a mono-periodic polymeric structure due to the bridging function of the dimethyl--benzoyl-amido-phosphate anions towards the caesium cations.

Crystal structure of bis-{3-(3,4-di-methyl-phen-yl)-5-[6-(1-pyrazol-1-yl)pyridin-2-yl]-4-1,2,4-triazol-4-ido}iron(II) methanol disolvate.

As a result of the high symmetry of the 2 structure, the asymmetric unit of the title compound, [Fe(CHN)]·2MeOH, consists of half of a charge-neutral complex mol-ecule and a discrete methanol mol-ecule. The planar anionic tridentate ligand 2-[5-(3,4-di-methyl-phen-yl)-4-1,2,4-triazol-3-ato]-6-(1-pyrazol-1-yl)pyridine coordinates the Fe ion meridionally through the N atoms of the pyrazole, pyridine and triazole groups, forming a pseudo-octa-hedral coordination sphere of the central ion. The average Fe-N bond distance is 1.

Crystal structure of bis-{3-(3-bromo-4-methoxyphenyl)-5-[6-(1-pyrazol-1-yl)pyridin-2-yl]-1,2,4-triazol-3-ato}-iron(II) methano-l disolvate.

The unit cell of the title compound, [Fe(CHBrNO)]·2MeOH, consists of a charge-neutral complex mol-ecule and two independent mol-ecules of methanol. In the complex mol-ecule, the two tridentate ligand mol-ecules 2-[5-(3-bromo-4-meth-oxy-phen-yl)-4-1,2,4-triazol-3-yl]-6-(1-pyrazol-1-yl)pyridine coordinate to the Fe ion through the N atoms of the pyrazole, pyridine and triazole groups, forming a pseudo-octa-hedral coordination sphere around the central ion. In the crystal, neighbouring asymmetric mol-ecules are linked through weak C-H(pz)⋯π(ph) inter-actions into chains, which are then linked into layers by weak C-H⋯N/C inter-actions.

New Luminescent Lanthanide Tetrakis-Complexes NEt [LnL ] Based on Dimethyl-N-Benzoylamidophosphate.

New lanthanide dimethyl-N-benzoylamidophosphate (HL) based tetrakis-complexes NEt [LnL ] (Ln =La, Nd, Sm, Eu, Gd, Tb, Dy) are reported. The complexes are characterized by means of NMR, IR, absorption, and luminescent spectroscopy as well as by elemental, X-Ray, and thermal gravimetric analyses. The phenyl groups of the four ligands of the complex anion are directed towards one side, while the methoxy groups are directed in the opposite side, which makes the complexes under consideration structurally similar to calixarenes.

Spectroscopic aspects for the Yb coordination compound with a large energy gap between the ligand and Yb excited states.

We present the experimental and theoretical results that made it possible to propose the energy transfer mechanism for a Yb complex with a large energy gap between the ligand and Yb excited states using a theoretical model and experimental data. Absorption and emission spectroscopy in the 300-4 K range is used for the study of the Yb compound with N-phosphorylated sulfonamide (Na[YbL]), which, despite the large energy gap, is characterized by high emission sensitization efficiency (η = 40%) and relatively long Yb emission lifetime (27 μs). The crystal structure of Na[YbL], radiative lifetime (930 μs), refractive index (1.

Crystal structure and Hirshfeld surface analysis of the anionic tetra-kis-complex of lanthanum(III) NMeLa with the CAPh-ligand dimeth-yl (2,2,2-tri-chloro-acet-yl)phospho-ramidate.

The anionic tetra-kis-complex of lanthanum(III) NMeLa with the CAPh-ligand dimethyl (2,2,2-tri-chloro-acet-yl)phospho-ramidate (H), namely, tetra-methyl-ammonium tetra-kis-{2,2,2-tri-chloro-1-[(di-meth-oxy-phosphor-yl)imino]-ethano-lato}lanthanum(III), (CHN)[La(CHClNOP)], has been synthesized, crystallized and structurally characterized by X-ray diffraction. The lanthanide ion is surrounded by four anionic, bis-chelating CAPh ligands forming the complex anion with a coordination number of eight for La and NMe as the counter-ion. The coordination polyhedron of the La ion was inter-preted as a triangular dodeca-hedron.

Crystal structure of { , -bis-[(1--butyl-1-1,2,3-triazol-4-yl)methyl-idene]-2,2-di-methyl-propane-1,3-di-amine}-bis-(thio-cyanato)-iron(II).

The unit cell of the title compound, [Fe(NCS)(CHN)], consists of two charge-neutral complex mol-ecules. In the complex mol-ecule, the tetra-dentate ligand -bis-[(1--butyl-1-1,2,3-triazol-4-yl)methyl-ene]-2,2-di-methyl-propane-1,3-di-amine coordinates to the Fe ion through the N atoms of the 1,2,3-triazole and aldimine groups. Two thio-cyanate anions, also coordinated through their N atoms, complete the coordination sphere of the central Fe ion.

Efficient Sensitized Luminescence of Binuclear Ln(III) Complexes Based on a Chelating Bis-Carbacylamidophosphate.

Binuclear rare earth complexes LnLphen (Ln = Nd, Sm, Eu, Tb, Dy, Yb and Y) with bis-CAPh type ligand - tetramethyl N,N'-(2,2,3,3,4,4-hexafluoro-1,5-dioxopentane-1,5-diyl)bis(phosphoramidate) (HL) and 1,10-phenanthroline (phen) were synthesized and characterized by elemental analysis, IR, NMR, absorption and luminescence spectroscopy. Luminescence measurements were performed for all the complexes in solid state and for the Eu, Tb and Y complexes - in solution in DMSO as well. The effective energy transfer from organic ligands to Ln ions strongly sensitizes the Ln ions emission and under excitation by UV light, the complexes exhibited bright characteristic emission of lanthanide metal centers.

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 (HL), and its sodium salt, NaHL, have been synthesized and their structural properties have been investigated. Coordination compounds of lanthanides [Ln(HL)NO]·i-PrOH (Ln = Eu, Tb) 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 HL behaves like a scorpionate type ligand and in a mono-deprotonated form coordinates in a tridentate manner the oxygen atoms of phosphoryl and carbonyl groups with formation of a mononuclear metal complex.

Crystal structure of the mixed methanol and ethanol solvate of bis-{3,4,5-trimeth-oxy-'-[1-(pyridin-2-yl)ethyl-idene]benzohydrazidato}zinc(II).

The unit cell of the title compound, [Zn(CHNO)]·CHO·CHO, contains two complex mol-ecules related by an inversion centre, plus one methanol and one ethanol solvent molecule per complex molecule. In each complex, two deprotonated pyridine aroylhydrazone ligands {3,4,5-trimeth-oxy-'-[1-(pyridin-2-yl)ethyl-idene]benzohydrazide} coordinate to the Zn ion through the N atoms of the pyridine group and the ketamine, and, additionally, through the O atom of the enolate group. In the crystal, dimers are formed by π-π inter-actions between the planar ligand moieties, which are further connected by C⋯O and C⋯C inter-actions.

Structures and Spectral and Magnetic Properties of a Series of Carbacylamidophosphate Pentanuclear Lanthanide(III) Hydroxo Complexes.

A series of pentanuclear lanthanide complexes LnL(μ-L)(μ-OH)(μ-OH) (Ln = Nd, Dy, Ho, Er, Yb; L = dimethyl -benzoylamidophosphate ion, [CHC(O)-N-P(O)(OCH)]) was obtained by the reaction of sodium dimethyl -benzoylamidophosphate with the corresponding lanthanide nitrates. The pentanuclear cores formed as a result of self-arrangement and their composition did not depend on the lanthanide ion. The complexes and sodium dimethyl -benzoylamidophosphate have been characterized by single-crystal X-ray diffraction.

Crystal structure of -(di-phenyl-phosphor-yl)-2-meth-oxy-benzamide.

In the title compound, CHNOP, the C=O and P=O groups of the carbacyl-amido-phosphate (CAPh) fragments are located in a synclinal position relative to each other and are pre-organized for bidentate chelate coordination of metal ions. The N-H group is involved in the formation of an intra-molecular hydrogen bond. In the crystal, mol-ecules do not form strong inter-molecular inter-actions but the mol-ecules are linked weak C-H⋯π inter-actions, forming chains along [001].

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.

Synthesis and Characterization of Anionic Lanthanide(III) Complexes with a Bidentate Sulfonylamidophosphate (SAPh) Ligand.

A series of new anionic lanthanide(III) complexes with the general formula NEt[Ln] (; H = dimethyl[(4-methylphenyl)sulfonyl]amidophosphate; Ln = La, Nd, Eu), were synthesized and characterized by IR, UV-vis, and NMR spectroscopies, the differential scanning calorimetry method, thermogravimetric and X-ray analysis, and photoluminescence measurements. Single-crystal structures of NEt[Eu] () were determined at 293 and 100 K and evidenced the phase transition. Both phases are in the monoclinic crystal system in centrosymmetric groups of the same Laue class.

C Fullerene Effects on Diphenyl-N-(trichloroacetyl)-amidophosphate Interaction with DNA In Silico and Its Cytotoxic Activity Against Human Leukemic Cell Line In Vitro.

New representative of carbacylamidophosphates - diphenyl-N-(trichloroacetyl)-amidophosphate (HL), which contains two phenoxy substituents near the phosphoryl group, was synthesized, identified by elemental analysis and IR and NMR spectroscopy, and tested as a cytotoxic agent itself and in combination with C fullerene.According to molecular simulation results, C fullerene and HL could interact with DNA and form a rigid complex stabilized by stacking interactions of HL phenyl groups with C fullerene and DNA G nucleotide, as well as by interactions of HL CCl group by ion-π bonds with C molecule and by electrostatic bonds with DNA G nucleotide.With the use of MTT test, the cytotoxic activity of HL against human leukemic CCRF-CM cells with IC value detected at 10 μM concentration at 72 h of cells treatment was shown.

Tris(-{bis-[meth-yl(phen-yl)amino]-phosphor-yl}benzene-sulfonamidato-κ,')(1,10-phenanthroline-κ,')lanthanum(III).

The asymmetric unit of [La(CHNOPS)(CHN)] is created by one La ion, three deprotonated -{bis-[meth-yl(phen-yl)amino]-phosphor-yl}benzene-sulfonamidate () ligands and one 1,10-phenanthroline (Phen) mol-ecule. Each La ion is eight-coordinated (6O+2N) by three phosphoryl O atoms, three sulfonyl O atoms of three ligands and two N atoms of the chelating Phen ligand, leading to the formation of six- and five-membered metallacycles, respectively. The lanthanum coordination polyhedron has a bicapped trigonal-prismatic geometry.

Cytotoxic Effects of Dimorfolido-N-Trichloroacetylphosphorylamide and Dimorfolido-N-Benzoylphosphorylamide in Combination with C Fullerene on Leukemic Cells and Docking Study of Their Interaction with DNA.

Dimorfolido-N-trichloroacetylphosphorylamide (HL1) and dimorfolido-N-benzoylphosphorylamide (HL2) as representatives of carbacylamidophosphates were synthesized and identified by the methods of IR, H, and P NMR spectroscopy. In vitro HL1 and HL2 at 1 mM concentration caused cell specific and time-dependent decrease of leukemic cell viability. Compounds caused the similar gradual decrease of Jurkat cells viability at 72 h (by 35%).

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

In the mol-ecular structure of the title compound, [CaNa(CHClNOP)(HO)], the Ca 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 CCl 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 -axis direction O-H⋯O hydrogen bonds that involve the coordinating water mol-ecules and the phosphoryl groups.

Contribution of Energy Transfer from the Singlet State to the Sensitization of Eu and Tb Luminescence by Sulfonylamidophosphates.

A series of stable lanthanide complexes Na[Ln(L) ] (Ln=La , Eu , Gd , Tb , with L=dimethyl(4-methylphenylsulfonyl)amidophosphate and dimethyl-2-naphthylsulfonylamidophosphate) were synthesized. The compounds were characterized by single-crystal X-ray diffraction, IR, absorption, and emission spectroscopy at 293 and 77 K. In contrast to the usual and well-known dominant role of the ligand triplet state in intramolecular energy transfer processes in Ln complexes, in this particular new class of Ln compounds with sulphonylamidophosphate ligands, strong experimental and detailed theoretical evidence suggest a dominant role is played by the ligand first excited singlet state.

COMPUTER PREDICTION OF BIOLOGICAL ACTIVITY OF DIMETHYL-N-(BENZOYL)AMIDOPHOSPHATE AND DIMETHYL-N-(PHENYLSULFONYL)AMIDOPHOSPHATE, EVALUATION OF THEIR CYTOTOXIC ACTIVITY AGAINST LEUKEMIC CELLS IN VITRO.

Structural analogues of β-diketones--dimethyl-N-(benzoyl)amidophosphate (HCP) and dimethyl-N-(phenylsulfonyl)amidophosphate (HSP) were synthesized and identified by the methods of IR, 1H and 31P NMR spectroscopy. Screening of biological activity and calculation of physicochemical parameters of HCP and HSP compounds were done with the use of PASS and ACD/Labs computer programs. A wide range of biological activity of synthesized compounds, antitumor activity in particular, has been found.