Vasyl Kinzhybalo

Synthesis, X-ray characterization, DFT calculations and Hirshfeld surface analysis of thiosemicarbazone complexes of Mn+ ions (n = 2, 3; M = Ni, Cd, Mn, Co and Cu)

Two new pyridine-based heterocyclic thiosemicarbazone ligands and their Ni(II), Cd(II), Mn(II), Co(III) and Cu(II) complexes have been synthesized and characterized by structural, analytical and spectroscopic methods. The monodeprotonated anionic forms of the ligands coordinate in a tridentate fashion via two nitrogen and one sulphur donor atoms to yield seven complexes in which metal centres vary from four-coordinated square planar to six-coordinated distorted octahedral geometries. Single-crystal X-ray crystallography showed that the molecular complexes can aggregate into larger entities depending on the anion coordinated to the metal centre. We have analysed the interesting supramolecular assemblies observed in the solid state of some complexes by means of DFT calculations. These assemblies are formed by a combination of several noncovalent interactions, including chelate ring–π, π–π, and chalcogen bonding interactions, that have been characterized using Baders Theory of “atoms-in-molecules”.

Electron density distribution in tetralithium hypodiphosphate hexahydrate, Li4P2O6·6H2O

Tetralithium hypodiphosphate hexahydrate, Li4P2O6·6H2O, forms a highly symmetrical crystal structure, where hypodiphosphate anions have \bar 3m (D3d) symmetry. Analysis of the charge distribution (experimental and theoretically calculated) shows that the charges of the P atoms are lower than in phosphates and phosphonates, whereas the O charges are similar. Values of both ρc and ∇(2)ρc suggest that the P-P bond is a weak covalent one, while the P-O one is polarized covalent, with topological parameters similar to those of P-O bonds in phosphates or phosphonates. Theoretical calculations show that the hypodiphosphate anion is relatively insensitive to its coordination environment; this is brought about by the vicinity of cationic P atoms. The localization and delocalization indices have been computed and discussed.

Aqua­(phthalocyaninato)magnesium n-propyl­amine disolvate

The crystals of the title compound, [Mg(C(32)H(16)N(8))(H(2)O)].2C(3)H(9)N, are built up from MgPc(H(2)O) [Pc is phthalocyaninate(2-)] and n-propylamine molecules that interact via O-H...N hydrogen bonds. The MgPc(H(2)O) molecule is non-planar. The central Mg atom is coordinated by the four equatorial isoindole N atoms of the Pc ring system and by the O atom of an axial water molecule. The Mg atom is displaced by 0.509 (1) A from the N(4) plane towards the water O atom. MgPc(H(2)O).2(n-propylamine) molecules related by the inversion centre are linked by N-H...O hydrogen bonds to form a dimeric aggregate.

Physical and Structural Characterization of Imidazolium-Based Organic–Inorganic Hybrid: (C3N2H5)2[CoCl4]

(C3N2H5)2[CoCl4] (ICC) was characterized in a wide temperature range by the single-crystal X-ray diffraction method. Differential scanning calorimetry revealed two structural phase transitions: continuous at 245.5 K (from phase I to II) and a discontinuous one at 234/237 K (cooling/heating) (II → III). ICC adopts monoclinic space groups C2/c and P21/c in phase (I) and (III), respectively. The intermediate phase (II) appears to be incommensurately modulated. Dynamic properties of polycrystalline ICC were studied by means of dielectric spectroscopy and proton magnetic resonance ((1)H NMR). The presence of a low frequency dielectric relaxation process in phase III reflects libration motion of the imidazolium cations. The temperature dependence of the (1)H spin-lattice relaxation time indicated two motional processes with similar activation energies that are by about an order of magnitude smaller than the activation energy obtained from dielectric studies. There are no abrupt changes in the (1)H relaxation time at the phase transitions indicating that the dynamics of the imidazolium rings gradually varies with temperature; that is, it does not change suddenly at the phase transition. Negative values of the Weiss constant and the intermolecular exchange parameter were obtained, confirming the presence of a weak antiferromagnetic interaction between the nearest cobalt centers. Moreover, the magnitude of zero field splitting was determined. The AC susceptibility measurements show that a slow magnetic relaxation is induced by small external magnetic field.

Crystal structure of tris­(piperidinium) hydrogen sulfate sulfate

A novel mixed hydrogen sulfate–sulfate piperidinium salt comprises three protonated piperidinium cations, one hydrogen sulfate anion and one sulfate anion in the asymmetric unit. Strong hydrogen bonds exist between the cations and the anions giving rise to a three-dimensional structure.

Reactions of N≡W(OtBu)3 and O=W(OiPr)4 with Low-Coordinate Phosphorus Compounds: Similarities and Differences

Abstract The reactions of N≡W(OtBu)3 and O=W(OiPr)4 with (Me3Si)2NPNSiMe3 (I), (Me3Si)2NPNtBu (II), and (Me3Si)2NP(NSiMe3)2 (III) in benzene have been studied. Low-coordinate phosphorus derivatives react with above mentioned tungsten compounds via 1,2-addition of an W-OR bond across the P=N bond, resulting in four-membered metallacycles. (Me3Si)2N-P(NSiMe3)2 reacts with O=W(OiPr)4 in a different manner via [2 + 2] cycloaddition. The structure of all new compounds was elucidated by 1H, 13C, and 31P NMR spectroscopy. Compound [(Me3Si)2N-P(NSiMe3)2(O)]{W(OiPr)4} (6) was also characterized by single crystal X-ray analysis.

Synthesis, structure and characterization of five new organically templated metal sulfates with 2-aminopyridinium.

The chemistry of organically templated metal sulfates has attracted interest from the materials science community and the development of synthetic strategies for the preparation of organic-inorganic hybrid materials with novel structures and special properties is of current interest. Sulfur-oxygen-metal linkages provide the possibility of using sulfate tetrahedra as building units to form new solid-state materials. A series of novel organically templated metal sulfates of 2-aminopyridinium (2ap) with aluminium(III), cobalt(II), magnesium(II), nickel(II) and zinc(II) were obtained from the respective aqueous solutions and studied by single-crystal X-ray diffraction. The compounds crystallize in centrosymmetric triclinic unit cells in three structure types: type 1 for 2-aminopyridinium hexaaquaaluminium(III) bis(sulfate) tetrahydrate, (C5H7N2)[Al(H2O)6](SO4)2·4H2O, (I); type 2 for bis(2-aminopyridinium) tris[hexaaquacobalt(II)] tetrakis(sulfate) dihydrate, (C5H7N2)2[Co(H2O)6]3(SO4)4·2H2O, (II), and bis(2-aminopyridinium) tris[hexaaquamagnesium(II)] tetrakis(sulfate) dihydrate, (C5H7N2)2[Mg(H2O)6]3(SO4)4·2H2O, (III); and type 3 for bis(2-aminopyridinium) hexaaquanickel(II) bis(sulfate), (C5H7N2)2[Ni(H2O)6](SO4)2, (IV), and bis(2-aminopyridinium) hexaaquazinc(II) bis(sulfate), (C5H7N2)2[Zn(H2O)6](SO4)2, (V). The templating role of the 2ap cation in all of the reported crystalline substances is governed by the formation of characteristic charge-assisted hydrogen-bonded pairs with sulfate anions and the presence of π-π interactions between the cations. Additionally, both coordinated and uncoordinated water molecules are involved in hydrogen-bond formation. As a consequence, extensive three-dimensional hydrogen-bonding patterns are formed in the reported crystal structures.

Crystal structure of new organically templated copper sulfate with 2-amino­pyridinium

The title compound, (C5H7N2)2[Cu(H2O)6](SO4)2·4H2O [systematic name: bis(2-aminopyridinium) hexaaquacopper(II) bis(sulfate) tetrahydrate], comprises axially elongated hexaaqua-coordinated octahedral CuII ions located on an inversion centre, non-coordinating sulfate anions, 2-aminopyridinium cations and lattice water molecules. The crystal structure is built of successive inorganic and organic layers extending parallel to (001) that are connected by an extensive three-dimensional hydrogen-bonded network of the type O—H⋯O and N—H⋯O, as well as π–π interactions [centroid–centroid distance 3.4140 (14) Å, offset 0.277 Å].

Reactions of (iPrO)3MM(OiPr)3 (M = Mo, W) with low-coordinate phosphorus compounds. Formation of the first four-membered planar metallacycles, containing an MM triple bond

The low-coordinate phosphorus compounds (Me(3)Si)(2)N-P=NSiMe(3), (Me(3)Si)(2)N-P(=S)=N(t)Bu and (Me(3)Si)(2)N-P(=NSiMe(3))(2) react with ((i)PrO)(3)M≡M(O(i)Pr)(3) (M = Mo, W) to form four- and five-membered metallacycles with intact endocyclic or exocyclic M≡M triple bonds. The first four-membered planar metallacycles, containing an M≡M triple bond were obtained in reaction with (Me(3)Si)(2)N-P=NSiMe(3).

Ferroelasticity and piezoelectricity of organic–inorganic hybrid materials with a one-dimensional anionic structure: so similar, yet so different

The synthesis, structural aspects, thermal and dielectric analysis for new members of the ferroic family, polynuclear Bi(III) and Sb(III) halide complexes based on a pyrazolium cation with the formulas (C3N2H5)[BiCl4]·H2O and (C3N2H5)[SbCl4]·H2O, are presented. The former compound was found to undergo a ferroic phase transition of the ferroelastic type at 213/219 K (cooling/heating scans), whereas, the latter one exhibited a piezoelectric feature in the dielectric response function. The molecular motions of pyrazolium cations were analyzed based on the spin–lattice relaxation time of 1H NMR measurements.