Showing papers by "Andrey V. Gerasimenko published in 2008"

Synthesis, structural and multinuclear natural abundance (13C, 31P, 195Pt) CP/MAS NMR studies of crystalline O,O′-dialkyldithiophosphate platinum(II) complexes

Abstract: Platinum(II) O,O′-dicyclohexyl dithiophosphate [Pt{S2P(O-cyclo-C6H11)2}2] (I) and platinum(II) O,O′-diisopropyl dithiophosphate [Pt{S2P(O-iso-C3H7)2}2] (II) complexes were obtained and studied by solidstate 13C, 31P, and 195Pt CP/MAS NMR spectroscopy. The dithiophosphate (Dtph) ligands in molecular structure I were found to be coordinated by platinum in S,S′-bidentate fashion to form the planar chromophore [PtS4] (single-crystal X-ray diffraction data). For complex II, a new α-form (α-II) was obtained and identified by 31P MAS NMR spectroscopy. The 31P chemical shift anisotropy δaniso and the asymmetry parameter η of the 31P chemical shift tensor were calculated from the whole MAS spectra.

Disordering of the [NbOF5]2− complex anions in bis(glycinium) pentafluoridooxidoniobate(V) and bis(β‐alaninium) pentafluoridooxidoniobate(V) dihydrate

Abstract: The title compounds, (C2H6NO2)2[NbOF5], (I), and (C3H8NO2)2[NbOF5]·2H2O, (II), are built from isolated distorted octa­hedral [NbOF5]2− complex anions, amino acid cations and water mol­ecules [for (II)]. In the penta­fluorido­oxido­nio­bate(V) anions, the Nb and O atoms, and the F atoms in trans positions with respect to the O atoms, are disordered about an inversion centre for both structures. The Nb atoms are shifted from the inversion centres by distances of 0.1455 (1) and 0.1263 (2) A for (I) and (II), respectively. The Nb=O and Nb—F(trans) bond lengths are 1.7952 (3) and 2.0862 (3) A, respectively, for (I), and 1.8037 (7) and 2.0556 (7) A for (II). In the crystal structures, cations and water mol­ecules [for (II)] are linked to the [NbOF5]2− anions via hydrogen bonds. This study demonstrates the possibility of true geometry determination of disordered [NbOF5]2− complex anions in centrosymmetric structures.

Tetraphenylantimony(V) O,O′-dialkyl dithiophosphates [Sb(C6H5)4{S2P(OR)2}] (R = s-C4H9, c-C6H11): Synthesis, structures, and 13C and 31P CP/MAS NMR spectra

Abstract: Tetraphenylantimony(V) O,O′-di-sec-butyl dithiophosphate (I) and tetraphenylantimony(V) O,O′-dicyclohexyl dithiophosphate (II) [Sb(C 6H5)4{S2P(OR)2}] (R = sec-C4H9 or cyclo-C6H11) were obtained. Th ...

Chemisorption of copper(II) at zinc and cadmium dialkyldithiocarbamates: EPR and X-ray diffraction studies

Abstract: Chemisorption of Cu2+ cations at zinc and cadmium dialkyldithiocarbamates was studied. According to EPR data, in the first step, the zinc and cadmium atoms are partially replaced by copper in the starting molecular structure to form heterobinuclear and heteropolynuclear complexes. In the second step, copper replaces up to 90 to 97% of the total number of the metal atoms, yielding binuclear and polynuclear copper(II) complexes. The possibility of the existence of heterobinuclear complexes in the individual state was demonstrated with [CuCd{S2CN(C2H5)2}4] as an example. Its molecular and crystal structures were determined from X-ray diffraction data.

Bis(dihydrogen norfloxacinium) tri-μ2-chlorido-bis­[trichloridobismuthate(III)] chloride dihydrate

Abstract: The title compound, {systematic name: (3-carb­oxy-1-ethyl-6-fluoro-7-piperazin-4-ium-1-yl-1H-quinolin-4-yl­idene)oxonium tri-μ2-chlorido-bis­[trichloridobismuthate(III)] chloride dihydrate], (C16H20FN3O3)2[Bi2Cl9]Cl·2H2O, is composed of [Bi2Cl9]3− anions lying on crystallographic twofold rotation axes, Cl− anions also on twofold axes, C16H20FN3O32+ cations, and water mol­ecules. The BiIII coordination polyhedron is a distorted octa­hedron and two such octa­hedra share a triangular face to form the complex anion. There are three short terminal Bi—Cl bonds [2.5471 (6)–2.5781(5 A] and three longer bridging bonds [2.8599 (5)–2.9984 (6) A] in each octa­hedron. Anions, cations and water mol­ecules are linked by hydrogen bonds to form a three-dimensional network. There are also π–π stacking inter­actions between quinoline ring systems, with an inter­planar distance of 3.27 (1) A.

Synthesis and structure of the polynuclear thallium(I) N,N-cyclo -pentamethylenedithiocarbamate complex [Tl 2 {S 2 CN(CH 2 ) 5 } 2 ] n as probed by single-crystal X-ray diffraction and 13 C and 15 N CP/MAS NMR: An example of complicated structural organization

Abstract: Synthesis and structure of the polynuclear thallium(I) N,N-cyclo-pentamethylenedithiocarbamate complex [Tl-2{S2CN(CH2)(5)}(2)](n) as probed by single-crystal X-ray diffraction and C-13 and N-15 CP/MAS NMR : an example of complicated structural organization

Tetra­kis(dihydrogen pefloxacinium) di-μ2-chlorido-bis­[tetra­chloridobismuthate(III)] tetra­chloride octa­hydrate

Abstract: The title compound {systematic name: tetra­kis[4-(3-carb­oxy-1-ethyl-6-fluoro-4-hydroxonio-1,4-dihydro-7-quinol­yl)-1-meth­yl­piperazin-1-ium] di-μ2-chlorido-bis­[tetra­chlorido­bismuth­ate(III)] tetra­chloride octa­hydrate}, (C17H22FN3O3)4[Bi2Cl10]Cl4·8H2O, is composed of edge-shared centrosymmetric dinuclear [Bi2Cl10]4− anions, Cl− anions, dihydrogen pefloxacinium cations and water mol­ecules. The BiIII coordination polyhedron is a distorted octa­hedron. There are four short terminal Bi—Cl bonds [2.5037 (10)–2.6911 (7) A] and two longer bridging bonds [2.8834 (8) and 3.0687 (9) A] in each octa­hedron. Two sets of chloride ions and water mol­ecules are disordered over the same sites with site occupancies of 1/3 and 2/3, respectively. Anions, cations and water mol­ecules are linked by O—H⋯O, O—H⋯Cl and N—H⋯Cl hydrogen bonds, forming a three-dimensional framework. There are also π–π stacking inter­actions between quinoline ring systems [centroid–centroid distance = 3.575 (1) A].

Adducts of zinc and copper(II) dimethyland diethyldithiocarbamates with piperidine: Synthesis, EPR, solid-state natural abundance 13C and 15N CP/MAS NMR and single-crystal X-ray diffraction studies

Abstract: Crystalline adducts of zinc and copper(II) dimethyl-and diethyldithiocarbamates with piperidine (Pip) of the general formula [M{NH(CH2)5}(S2CNR2)2] (M = Zn and 63Cu; R = CH3 and C2H5) were obtained. Their structures and spectroscopic characteristics were studied by X-ray diffraction analysis, EPR spectroscopy, and solid-state natural abundance 13C and 15N MAS NMR spectroscopy. The most substantial differences between the adducts of the formula [Zn{NH(CH2)5}(S2CNR2)2] (R = CH3 and C2H5) were found in the spatial orientations of the coordinated heterocycles and the geometries of the zinc polyhedra. The individual character of the EPR spectra of magnetically diluted isotope-substituted copper(II) adducts was determined by computerassisted modeling. The adducts of copper(II) and zinc dimethyldithiocarbamates proved to exist as two isomers. The coordination polyhedra of copper(II) and zinc are intermediate between a tetragonal pyramid (TP) and a trigonal bipyramid (TBP). The contributions from the TBP/TP components to the coordination polyhedra were quantitatively estimated from X-ray diffraction data. The 13C and 15N NMR signals were assigned to the positions of the atoms of the =NC(S)S− groups in the resolved (according to X-ray diffraction data) molecular structures of the adducts.

Crystal structure and spectroscopic properties of ciprofloxacinium pentachloroantimonate(III) monohydrate (C17H19N3O3F)SbCl5 · H2O

Abstract: Synthesis, X-ray diffraction, IR and luminescence spectroscopic studies of the monohydrate of pentachloroantimonate(III) of doubly protonated ciprofloxacin (C17H19N3O3F)SbCl5 · H2O (I) were performed. The structure of I is formed by SbCl6 octahedra combined into polymeric chains [SbCl5]n2n− through common vertices, ciprofloxacinium cations (CfH3)2+, and water molecules linked by hydrogen bonds. CfH is protonated at the carbonyl oxygen atom and the terminal nitrogen atom of the piperazinyl group. The electronic and geometric aspects determining the luminescence properties of I and of related compounds are discussed.

Structural organization of the tetranuclear zinc di-iso-propyl phosphorodithioate complex [Zn4O{S2P(O-iso-C3H7))2}6] as probed by single-crystal x-ray diffraction and 13C and 31P CP/MAS NMR

Abstract: The zinc O,O’-di-iso-propyl phosphorodithioate complex [Zn4O⨑ub;S2P(O-iso-C3H7)2⫂ub;6] (I) has been synthesized and characterized by multinuclear MAS NMR (13C, 31P). The metal core of the tetranuclear structure of I, determined by single-crystal X-ray diffraction, is a tetrahedron centered by an oxygen atom. All Dtph ligands are structurally nonequivalent and act as μ2 bridges combining pairs of zinc atoms. Bonding of all metal atoms to the μ4 oxygen atom provides additional stabilization of the structure. For 31P NMR signals, the chemical shift anisotropy δaniso and the asymmetry parameter η were calculated, which allowed to assign them to the phosphorus positions in the structure of I.

Synthesis, Molecular Structure, and Thermal Properties of the Supramolecular Complex [Zn{NH(CH2)4O}{S2CN(C2H5)2}2]2 · CH2N(CH2)4O}2

Abstract: The supramolecular complex [Zn{NH(CH2)4O}{S2CN(C2H5)2}2]2 · CH2N(CH2)4O}2 (I) has been synthesized and studied by X-ray crystallography and thermal analysis. The noncentrosymmetric complex is composed of two structurally nonequivalent molecules of the adduct of bis(diethyldithiocarbamato)zinc with morpholine, which are linked with the outer-sphere N,N’-dimorpholinomethane molecule through two hydrogen bonds N-H⋯O. The major differences between the adduct molecules are related to the strength of Zn-N bonds, spatial orientation of the coordinated morpholine heterocyclic rings, and the proportion between the contributions of the trigonal bipyramidal (TBP) and tetragonal pyramidal (TP) components to the geometry of zinc polyhedra. Calculations show that the geometry of the zinc polyhedra is almost halfway between TBP and TP. The thermal destruction of supramolecular compound I is accompanied by desorption of the outer-sphere and coordinated organic molecules. At the final stage, defragmentation of the “dithiocarbamate part” of the complex leads to the formation of ZnS.

Synthesis and structure of nalidixium tetrachloroantimonate monohydrate, (C12H13N2O3)SbCl4 · H2O

Abstract: Nalidixium tetrachloroantimonate monohydrate, (C12H13N2O3)SbCl4 · H2O, has been synthesized and its crystal structure has been determined. The structure is built of the [Sb2Cl8]2− anions, C12H13N2O 3 + nalidixium cations, and H2O molecules joint by hydrogen bonds and π-π-and Cl⋯Cl interactions. The [Sb2Cl8]2− anion is a dimer of the SbCl5 E distorted octahedra sharing common Cl⋯Cl edge (E is the lone electron pair). The Sb polyhedra contain two short Sb-Cl bonds (2.387 and 2.395 A), one bond of a medium length (2.508 A), and two long bridging bonds (2.745 and 3.054 A).

Crystalline platinum(II) O,O′-di-iso-butyldithiophosphate as a Model of the structural state of platinum in cooperite: Synthesis, structure, and multinuclear 13C, 31P, and 195Pt MAS NMR

Abstract: Crystalline platinum(II) O,O'-di-iso-butyldithiophosphate as a model of the structural state of platinum in cooperite : synthesis, structure, and multinuclear 13C, p31P, and 195Pt MAS NMR