Crystal structure and supra-molecular features of bis-{ethyl 2-[1-methyl-3-(pyridin-2-yl)-1-1,2,4-triazol-5-yl]acetate}-tri-nitratolanthanum(III).

The title lanthanum(III) complex, [La(Et-MPTA)(NO)] {where Et-MPTA is ethyl 2-[1-methyl-3-(pyridin-2-yl)-1-1,2,4-triazol-5-yl]acetate} or [La(CHNO)(NO)], crystallizes in the monoclinic space group 2/ (No. 15). The lanthanum atom is twelve-coordinate, bonded to two oxygen atoms from carboxyl-ate groups, four nitro-gen atoms from two pyridinyl-1,2,4-triazole ligands, and six oxygen atoms of three NO anions.

Dual Visible and NIR Emission, Mechanoluminescence, and Magnetic Properties of PPh[L] Chelates with Diphenyl-N-Benzoylamidophosphate.

The design, synthesis, and study of lanthanide coordination compounds with luminescent and magnetic properties attractive in modern technologies is still a pressing and challenging task. In the present work, a series of coordination compounds of tetrakis-carbacylamidophosphate (where HL = diphenyl-N-benzoylamidophosphate) with several lanthanide ions such as , , , and was prepared and studied by X-ray analysis and luminescence spectroscopy at 293 and 77 K, as well as by magnetic measurements. Coordination compounds are not isostructural, but the type of coordination is the same.

Synthesis, structures and Hirshfeld surface analyses of 2-hy-droxy-'-methyl-acetohydrazide and 2-hy-droxy--methyl-acetohydrazide.

The structures of the title compounds 2-hy-droxy-'-methyl-acetohydrazide, , and 2-hy-droxy--methyl-acetohydrazide, , both CHNO, as regioisomers differ in the position of the methyl group relative to the N atoms in 2-hy-droxy-acetohydrazide. In the structure of , the 2-hy-droxy-acetohydrazide core [OH-C-C(=O)-NH-NH] is almost planar and the methyl group is rotated relative to this plane. As opposed to , in the structure of all non-hydrogen atoms lie in the same plane.

Crystal structure and Hirshfeld surface analysis of di-chlorido-[2-(3-cyclo-pentyl-1,2,4-triazol-5-yl-κ )pyridine-κ]palladium(II) di-methyl-formamide monosolvate.

This study presents the synthesis, characterization and Hirshfeld surface analysis of the title mononuclear complex, [PdCl(CHN)]·CHNO. The compound crystalizes in the 2/ space group of the monoclinic system. The asymmetric unit contains one neutral complex Pd(H )Cl [H is 2-(3-cyclo-pentyl-1,2,4-triazol-5-yl)pyridine] and one mol-ecule of DMF as a solvate.

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 and Hirshfeld surface analysis of bis-(μ-4--but-oxy-4-oxobut-2-en-2-olato)bis-[(4--but-oxy-4-oxobut-2-en-2-olato)ethano-lzinc(II)].

The mol-ecular and crystal structure of the title binuclear Zn complex, [Zn(CHO)(CHOH)], with enolated anionic -butyl-aceto-acetate and ethanol was analysed. The coordination polyhedra of the Zn atoms are distorted octa-hedra formed by six oxygen atoms that belong to three ligand mol-ecules and a coordinated ethanol mol-ecule. In the crystal phase, alternating layers can be distinguished parallel to the plane.

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.

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.

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.

Fluorenonophane chloro-benzene solvate: mol-ecular and crystal structures.

The title compound, 1 ,7 -3,5,9,11-tetra-oxa-1,7(2,7)-difluorena-4,10(1,3)-dibenzena-cyclo-dodeca-phane-1,7-dione (fluorenonophane), exists as a solvate with chloro-benzene, CHO·CHCl. The fluorenonophane contains two fluorenone fragments linked by two -substituted benzene fragments. Some decrease in its macrocyclic cavity leads to a stacking inter-action between the tricyclic fluorenone fragments.

Crystal structure of bis-[-di-aqua-bis-(phen-an-thro-line)cobalt(II)] bis-(citrato)germanate(IV) dinitrate.

The asymmetric unit of the title compound, [Co(CHN)(HO)][Ge(CHO)](NO), features two complex [(CHN)(HO)Co] cations, two NO anions as well as one centrosymmetric [(CHO)Ge] anion. Two HCit ligands (Cit = citrate, CHO) each coordinate three different oxygen atoms (hy-droxy-late, α-carboxyl-ate, β-carboxyl-ate) to the Ge atom, forming a slightly distorted octa-hedron. The coordination polyhedron of the Co atom is also octa-hedral, formed by coordination of four nitro-gen atoms from two phenanthroline mol-ecules and two water oxygen atoms.

Inherently chiral dialkyloxy-calix[4]arene acetic acids as enantiodiscriminating additives for high-performance liquid chromatography separation of d,l-amino acids.

Inherently chiral dialkyloxy-calix[4]arene acetic acids with asymmetric placement of substituents on the lower rim of the macrocycle were first studied as enantiodiscriminating additives to the mobile phase MeCN/H O/HCOOH (75/25/0.02 by volume) in the high-performance liquid chromatography (HPLC) separation of d,l-alanine and d,l-valine on the achiral stationary phase ZORBAX Original CN. The dependence of enantio-binding properties on the position of alkyl groups is demonstrated.

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.

In water multicomponent synthesis of low-molecular-mass 4,7-dihydrotetrazolo[1,5-]pyrimidines.

The three-component reaction of 5-aminotetrazole with aliphatic aldehydes (formaldehyde, acetaldehyde) and acetoacetic ester derivatives in water under microwave irradiation leads to the selective formation of 4,7-dihydrotetrazolo[1,5-]pyrimidine derivatives. Under similar conditions using 4,4,4-trifluoroacetoacetic ester 5-hydroxy-4,5,6,7-tetrahydrotetrazolo[1,5-]pyrimidines are obtained. The analogous reaction with acetylacetone requires scandium(III) triflate as catalyst.

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].

(μ-Methylenediphosphonato-κ ,':'',''')bis[(ethyl-ene-diamine-κ ,')palladium(II)] tetra-hydrate.

The title compound, [Pd(CHN)(CHOP)]·4HO, comprises of a binuclear mol-ecule (point group symmetry 2), with a twofold rotation axis running through the central C atom of the methyl-enedi-phospho-nate (MDP) anion. The Pd atom has a square-planar coordination environment defined by the N atoms of a bidentate ethyl-enedi-amine (en) ligand and two O atoms of the bridging MDP anion. In the crystal structure, metal complexes are arranged in layers parallel (001) and are sandwiched between layers containing disordered water mol-ecules of crystallization.

Expedited Route to Fully Substituted Amino-Pyrazole Building Blocks and Their Further Transformations.

We report here an efficient and easily reproducible two-step approach to heterocycle-substituted amino-pyrazoles from heterocyclic acetonitriles and their unprecedented subsequent transformations to fully substituted pyrazoles. Such transformations include regioselective derivatization from polyamino derivatives, formation of tetracyclic compounds in up to 45% overall yield, and deaminative transformations through diazotization, followed by arylation through Suzuki-Miyaura cross-coupling and C-H activation, providing arylated pyrazoles in up to 71% yield over four steps. This strategy allows the swift introduction of significant molecular complexity to a range of scaffolds.

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.

Supramolecular Architecture of Substituted Tetraphenyl-carbo-benzenes from the Energetic Viewpoint.

The use of DFT-calculated energy-vector diagrams (EVDs) featuring the topology of pairwise intermolecular interaction energies is applied to crystals of carbo-benzenes. A homogeneous set of six ideally centrosymmetric tetraphenyl-carbo-benzenes is selected, with various substituents R in para positions: R=4-anisyl, 1-ethyl-2-phenyl-1H-indol-3-yl, 2-chloro-2-(1-ethyl-2-phenyl-1H-indol-3-yl)ethenyl, tetradecyl, and 9,9-dihexyl-9H-fluoren-2-yl, 2-(9,9-dihexyl-9H-fluoren-2-yl)ethynyl. The basic structural motifs (BSMs) of the crystals vary from layers to columns, depending on the size and shape of the substituents R.

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.

Crystal structure of aqua-(nitrato-κO)dioxido{2-[3-(pyridin-2-yl-κN)-1H-1,2,4-triazol-5-yl-κN (4)]phenolato-κO}uranium(VI) aceto-nitrile monosolvate monohydrate.

In the title compound, [U(C13H9N4O)(NO3)O2(H2O)]·CH3CN·H2O, the U(VI) atom is seven-coordinated in a distorted penta-gonal-bipyramidal N2O5 manner by one tridentate triazole ligand, one monodentate nitrate anion and one water mol-ecule in the equatorial plane and by two uran-yl(VI) O atoms in the axial positions. In the crystal, the U(VI) complex mol-ecule is linked to the water and aceto-nitrile solvent mol-ecules through N-H⋯N, O-H⋯O and O-H⋯N hydrogen bonds, forming a sheet structure parallel to the bc plane. The sheets are further linked by an additional O-H⋯O hydrogen bond, forming a three-dimensional network.

Crystal structure of aqua-1κO-{μ-2-[(2-hydroxy-ethyl)methylamino]ethanolato-2:1κ(4) O (1),N,O (2):O (1)}[μ-2,2'-(methylimino)diethanolato-1:2κ(4) O,N,O':O]dithiocyanato-1κN,2κN-chromium(III)copper(II).

The title compound, [CrCu(C5H11NO2)(C5H12NO2)(NCS)2(H2O)] or [Cr(μ-mdea)Cu(μ-Hmdea)(NCS)2H2O], (where mdeaH2 is N-methylethanolamine, C5H13NO2) is formed as a neutral heterometal Cu(II)/Cr(III) complex. The mol-ecular structure of the complex is based on a binuclear {CuCr(μ-O)2} core. The coordination environment of each metal atom involves the N,O,O atoms of the tridentate ligand, one bridging O atom of the ligand and the N atom of the thio-cyanato ligands.

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.

Role of supramolecular synthons in the formation of the supramolecular architecture of molecular crystals revisited from an energetic viewpoint.

Analysis of the strengths and directionality of intermolecular interactions in the crystals containing only one type of supramolecular synthon allows the suggestion of a general classification of molecular crystals depending on type of their basic structural motifs. All crystals may be divided on four classes namely (I) crystals with isotropic packing of the building units; (II) columnar crystals where the basic structural motif (BSM) is a chain/column; (III) layered crystals with layers as the BSM; (IV) columnar-layered crystals containing chains/columns as the primary basic structural motif and layers as the secondary BSM. Taking into account the participation of different supramolecular synthons in the formation of different levels of the organization of molecular crystals, they may be considered as basic (responsible for the formation of molecular complexes as building units of crystals), primary, secondary and auxiliary, which are involved in the agglomeration of molecules in primary or secondary basic structural motifs or in the packing of these motifs, respectively.