Home – Home – Jornals – 2011 number 3

Two complexes [Zn(SALIMP)(CH₃CO₂)]₂ (1) and [Cu(SALIMP)Cl] (2) are obtained by the reactions of zinc(II) and copper(II) salts with a tridentate Schiff base ligand 2-[[(2-pyridinylmethyl)imino]methyl]phenol (HSALIMP). Their structure is determined by single crystal
X-ray diffraction. Data for complex 1: C₃₀H₂₈N₄O₆Zn₂, CCDC number: 668213, M_r = 671.3, monoclinic, C2/c, with a = 34.670(5) Å, b = 15.266(2) Å, c = 23.464(4) Å, β = 114.045(2)°, V = 11341(3) ų, Z = 16, F(000) = 5504, GOOF(F²) = 0.894, the final R = 0.0520 and wR =
= 0.1272 for 10515 observed reflections with I > 2σ(I); complex 2: C₁₃H₁₂N₂OClCu, CCDC number: 668211, M_r = 311.24, triclinic, P-1, with a = 7.4050(8) Å, b = 10.2369(11) Å, c = 16.2873(17) Å, α = 87.728(2)°, β = 87.818(2)°, γ = 78.279(2)°, V = 1207.4(2) ų, Z = 4, F(000) = 632, GOOF(F²) = 1.077, the final R = 0.0326 and wR = 0.0381 for 4209 observed reflections with I > 2σ(I).

The crystal and molecular structure of 2-ferrocenyl-2-propanol is studied by means of physicochemical methods. The compound crystallizes in the form of three crystallographically independent molecules with slightly different conformations. Crystals are monoclinic, C₁₃H₁₆FeO: a = 6.2687(7) Å, b = 36.614(4) Å, c = 15.291(2) Å; β = 97.86(2)°; V = 3477.2(7) ų, Z = 12, d_x = 1.396 g/cm³, P2₁/n space group. The molecule consists of the ferrocene fragment and the isopropyl carbinol substituent.

We present a thermogravimetric study of the thermolysis of trans-[Ru(NO)(NH₃)₄(H₂O)](HSO₄)SO₄ in a helium atmosphere. The intermediate product of thermolysis (at 186°C) is treated with a 2 M H₂SO₄ solution to obtain the first example of a sulfate ammine complex of nitrosoruthenium [Ru(NO)(NH₃)₄(SO₄)](HSO₄)·H₂O (I) with a ~70% yield. The product of higher temperature thermolysis (220°C) is treated with acids (H₂SO₄ and HCl) to obtain a triammine complex [Ru(NO)(NH₃)₃Cl(SO₄)]·2H₂O (II). The structure of the compounds is found by single crystal XRD: Pna2₁ space group, a = 10.8005(2) Å, b = 14.9032(3) Å, c = 7.7603(1) Å) (I) and P2₁/n space group, a = 8.9397(1) Å, b = 8.3276(1) Å, c = 13.8993(2) Å; β = 97.358(1)° (II).

A new 3-D europium sulfate Eu₂(H₂O)₄(SO₄)₃ 1 is synthesized solvothermally and characterized by single crystal X-ray diffraction, IR spectrum, TG, powder XRD, and ultraviolet excitation and emission spectrum. This compound crystallizes in the triclinic system with the space group P-1, a = 6.7520(9) Å, b = 9.1077(12) Å, c = 10.5910(14) Å, α = 94.432(2)°, β =
= 107.1170(10)°, γ = 99.160(2)°, V = 609.17(14) ų, Z = 2. The open framework of the title compound is an eight-membered ring channel along the crystallographic a-axis, which is built up by EuO₈ polyhedra and SO₄ tetrahedra.

The title compound 1′-Benzyl-8-(4-fluorobenzyl)-8-azaspiro[bicyclo[3.2.1] octane-3,4′-imidazolidine]-2′,5′-dione, C₂₃H₂₃FN₃O₂ is synthesized and the structure is investigated by X-ray diffraction studies. The compound crystallizes in the triclinic crystal class in the P1 space group. The hydantoin ring adopts a planar conformation and is affected by the π conjugation. The pyrrolidine and piperidine rings in the bicyclo octane moiety adopt envelope and chair conformations respectively. The structure exhibits both inter- and intramolecular hydrogen bonds of the type N-H…O, C-H…O, and C-H…N. The oxygen atom in the hydantoin ring simultaneously accepts two hydrogen bonds to form a three-centered hydrogen bonding pattern.

The phase diagram of the phloroglucinol (1,3,5-trioxybenzol)-dimethyl sulfoxide system is studied. The system is found to form a 1:1 molecular complex of phloroglucinol with dimethyl sulfoxide. The crystal structure of the complex is determined. The crystallographic data for C₈H₁₂O₄S, M = 204.24, monoclinic system, P2₁/n space group, unit cell parameters: a = 9.0345(2) Å, b = 9.6895(3) Å, c = 10.9960(3) Å, β = 98.865(1)°, V = 951.09(4) ų, Z = 4, d_x = 1.426 g/cm³, R1 = 0.0283, T = 150 K. The molecules are joined in a supramolecular ensemble via O-H⋯O hydrogen bonds.

FT-IR and photon correlation spectroscopy methods are used to study the distribution of free (bulk) and bound (hydration) water in Triton N-42 reverse micelles under the conditions of injection solubilization of hydrochloric acid solutions. The amount of each type of water is calculated depending on the solubilization capacity* (V_s /V_o) and HCl concentration in the aqueous pseudophase. According to the IR spectroscopy data, the distribution of water is largely determined by the solubilization capacity of the micellar solution, while the fraction of bulk water exceeds significantly the value calculated by the geometric approach based on the photon correlation spectroscopy data. The difference shows that there is bulk water in the surface layer formed by oxyethyl groups of Triton N-42 molecules in spherocylindrical micelles.

FT-IR spectroscopy is used to study the distribution of bulk (free) and hydration (bound) water during the extraction of Pt(IV) and Au(III) from acid sulfate-chloride media by Triton N-42 reverse micelles. The bulk water fraction in Triton N-42 micelles reduces from 44% to 23% with an increase in the sodium sulfate concentration up to 3.5 mol/l in the feed. A decrease in the total concentration of micellar water and bulk water fraction complies well with an increase in the Pt(IV) and Au(III) distribution coefficients and concentration during the extraction by Triton N-42 reverse micelles.

By X-ray diffraction the crystal and molecular structure of N-(1-silatranylmethyl)phthalimide (SMP) is determined. The coordination polyhedron of the silicon atom in SMP, as in all silatranes, is a trigonal bipyramide; the phthalimide cycle is planar. The data presented indicate that the silatranylmethyl group almost does not affect the geometry of the phthalimide moiety.

2-(4-chlorophenyl)-5,7-dimethoxyquinolin-4-yl phenyl bis(2-chloroethyl)phosphoramidate is synthesized and characterized by NMR, IR and single crystal X-ray crystallography. The crystal is triclinic, P1 space group, with a = 9.5188(19), b = 12.856(3), c = 13.250(3) Å, V =
= 1412.0(5) Å)³, and Z = 2 (at 291(2) K). The crystal packing arrangement indicates that the molecule is stacked through π…π aromatic stacking interactions.

A general approach to the solution of the electronic vibrational problem with imposed conditions on possible vibrational nuclear motions in a double-minimum potential well is proposed.

The quantum chemical (U)B3LYP/6-31G(d₅,p) method is used to determine the structural parameters and ionization potentials of aluminum(III) (μ-oxo)bis[phthalocyaninate] and monophthalocyaninate PcAlCl. Two (PcAl)₂O structures with similar energies are obtained: an eclipsed high-symmetry (D_4h) structure with a rectangular AlOAl group and a retarded low-symmetry (C_s) structure with the AlOAl bond angle of 167.5°. The AlO bonds include a substantial π component. The energy needed for the detachment of two electrons from a free (PcAl)₂O molecule is 13.46 eV.

Data of ¹³С NMR and quantum chemical methods is used to show that a change in the oxidation degree of 12-nuclear rhenium cluster complexes [Re₁₂CS₁₇(CN)₆]^n- from n = 6 to n = 8 leads to electron vacancy localization on the rhenium atoms surrounding the central carbon atom.

Two isostructural compounds (C₁₇H₂₂FN₃O₃)[MCl₄]·H₂O (M = Cd, Hg), C₁₇H₂₀FN₃O₃ is 1-ethyl-N-methyl-6-fluoride-1,4-dihydro-4-oxo-7-(4-methyl-1-piperazinyl)-3-quinoline carboxylic acid (PefH, pefloxacin), are synthesized and their crystal structure is determined. The crystals contain PefH₃²⁺ and MCL₄^2- ions. The neighboring [MCl₄]^2- ions are bonded together by two bridging water molecules through four Cl⋯(H-O-H)₂⋯Cl hydrogen bonds with the formation of the supramolecular motif R₂⁴(8) The supramolecular architecture of crystals is analyzed.

The cocrystallization method is used to obtain a new volatile heterometallic complex of the composition [Cu(ki)₂·Pb(hfa)₂]₂, where ki = 2-iminopentan-4-onate and hfa = hexafluoroacetylacetonate. The crystallographic data for C₂₀H₁₈CuF₁₂N₂O₆Pb: a = 10.6729(5) Å, b = 10.7712(5) Å, c = 13.4779(5) Å; α = 79.1020(10)°, β = 84.5140(10)°, γ = 66.2470(10)°, Р-1 space group, Z = 2, d_x = 2.102 g/cm³. The compound has a molecular structure built of individual Cu…Pb…Pb…Cu-type tetramers. The Cu…Pb and Pb…Pb distances in the tetramer are 3.454 Å and 4.122 Å respectively; the Cu-Pb-Pb angle is 160.7°.

The interaction of Ta₂O₅ with sodium hydroxide at 400°C yields Na₈[Ta₆O₁₉], which can be recrystallized from an aqueous solution in the form of Na₈[Ta₆O₁₉]·24.5H₂O. The complex is characterized by IR spectroscopy, thermogravimetry, powder XRD, and single crystal XRD: hexagonal system, P6₃ space group, a = 12.3622(2) Å, c = 31.4305(7) Å, V = 4159.81(13) ų, d_x = 3.217 g/cm³, R = 0.0195.

Two new linear Cu^II complexes [Cu(L¹)₂] (I) (HL¹ = (E)-3,5-dichloro-2-hydroxy benzaldehyde O-methyl oxime) and [Cu(L²)₂] (II) (HL² = (E)-3,5-dichloro-2-hydroxy benzaldehyde
O-ethyl oxime) are synthesized and characterized by elemental analysis, IR, UV-Vis, and
X-ray diffraction methods. X-ray crystallographic analyses indicate that complexes I and II have a similar structure consisting of one Cu^II ion and two L^- units. In the complexes, the Cu^II ion lying on an inversion centre is four-coordinated in a trans-CuN₂O₂ square planar geometry by two phenolate O and two oxime N atoms from two symmetry-related N,O-bidentate oxime-type ligands. However, the crystal structure of the two complexes is different: complex I forms an infinite three-dimensional supramolecular network structure through intermolecular hydrogen bonding and π⋯π interaction, while complex II forms an infinite one-dimensional supramolecular structure through intermolecular hydrogen bonds.

A mixed-ligand silver(I) complex of triphenylphosphine and N,N′-dibutylthiourea (Dbtu), [Ag(Ph₃P)₂(Dbtu)₂]NO₃, is prepared and its structure in the solid state is determined by X-ray crystallography. X-ray structure of this complex shows that it is mononuclear with the silver atom coordinated by two PPh₃ and two dibutylthiourea ligands adopting a distorted tetrahedral geometry. The crystal structure shows the formation of 1-D chains through intermolecular hydrogen bonding interactions between N-H of Dbtu and nitrate ions. The new complex is also characterized by IR and NMR (¹H and ³¹P) spectroscopy. The spectroscopic data are discussed in terms of the nature of bonding. A similar mixed-ligand complex is also prepared for tetramethylthiourea (Tmtu), but the structure of the resulting compound shows that it is a bis(phosphine) complex, [Ag(PPh₃)₂NO₃] rather than a mixed-ligand complex.

The molecular and crystal structure of methyl 1-isopropenyl-5a,5b,8,8,14a-pentamethyl-1,2,3,3a,4,5,5a,5b, 6,7,7a,8,9,14,14a,14b,15,16,16a,16b-icosahydrocyclopenta-[7,8]phenenthro[2,1-b]carbazole-3a-carboxylate is determined. Compound C₃₇H₅₁NO₂ II crystallizes in the C2 chiral space group: a = 27.0380(5) Å, b = 7.9817(15) Å, c = 18.1980(3) Å, β = 123.580(3)°.

The complex of 2-ethylthio-4,5-benzo-1,3-thiazole with CoCl₂ of the 2:1 composition is synthesized. By X-ray diffraction, its crystal and molecular structure is determined. The coordination polyhedron of the cobalt atom is a tetrahedron formed from two chlorine and two nitrogen atoms. The nitrogen atoms belong to two ligand conformations of the studied complex

The composition of the coordination polyhedron of the complex of copper(II) acetate with 2-[2-hydroxyphenyl]-4,4-diphenyl-1,2-dihydro-4H-3,1-benzoxazine in the solid state and solutions of ethanol and chloroform is studied. Using the angular overlap model, the interaction energy of the copper(II) ion with donor atoms of the ligand is calculated. The temperature dependence of the molar magnetic susceptibility (χ_М) of the complex in the solid state is studied; the occurrence of the exchange interaction of the antiferromagnetic type between two copper ions is found (2J = -57.8 cm^-1).

The adduct of 2-aminobenzothiazole (1) and 2-hydroxy-3-naphthoic acid (2) is synthesized by the normal temperature volatilization method. The crystal belongs to the monoclinic system, P2₁/c space group. It crystallizes with two independent molecules in the unit, the two independent molecules forming helices through hydrogen bonds. The luminescence property of 1, 2, and the adduct (1·2) were studied at room temperature.

The electronic structure, geometry, and thermodynamic parameters of the high-energy states of NO₃ and the (NO)₂ dimer are calculated at the DFT B3LYP/6-311++G(3df) level within the symmetrized Kohn-Sham formalism. The results of the DFT calculation of the excited states of NO₃ well agree with the experimental data and precise ab initio calculations. The reactivity of high-energy nitrogen trioxide in the activation of molecular nitrogen and nitrogen protoxide is analyzed. The assumption is substantiated that the Karavaev effect (gain of nitrogen oxides in an air mixture with nitric acid vapors) is due to the photochemical activation of molecular nitrogen in the presence of an NO₃ high-energy state as a decomposition product of nitric acid.

By means of the formula that characterizes the correlation between the parameters of XH…Y linear fragments ( are the bond lengths in free molecules, b^XHX, b^YHY are the dimensional coefficients) r^XX(r^XH) and r^XY(r^YH) dependences are obtained. Given the length of a hydrogen bridge formed by O, N, and F atoms, they enable us to find the proton position in the bridge. The definition "a quasi-symmetric hydrogen bond," based on the invariance of the r^XX distance when the proton shifts by 0.1 Å, is established to be applicable to ОНО, FHF, NHN, and ClHCl fragments. It is shown that the hydrogen bridge length remains almost constant (exceeds the minimum length by no more than 0.1 Å) if its bond orders are above 0.1. Here the displacement of the central proton can reach 0.2-0.3 Å.

This work deals with the interaction between urea and DNA bases (adenine, thymine, guanine, and cytosine). The optimized geometries, binding energies, and harmonic vibrational frequencies are calculated using the DFT/B3LYP functional combined with the 6-31+G(d,p) basis set. Their interactions are studied aiming to understand more about the nature of the intercalation binding forces between urea and DNA. Fourteen stable complexes are found on the potential energy surface. The structures are cyclic; they are stabilized by NH…O/N and CH…O interactions. The binding energies range from -19.9 kJ·mol^-1 to -74.0 kJ·mol^-1. The obtained formation energies indicate that Urea:G and Urea:C are more favorable than Urea:T and Urea:A.
In addition, the Atoms in Molecules theory is performed to study the hydrogen bonds in the complexes.

The structures and conformational stabilities of phenylphosphonic and phenylthiophosphonic acids are investigated using calculations mostly at the DFT/6-311G** level and ab initio ones at the MP2/6-311G** level (no frequency calculations in the latter case), because we know from our previous results that the addition of diffuse functions to a valence triple zeta basis with polarization functions might lead to an unbalanced basis set. Further, the experience tells that for large energy differences between conformers, DFT works very well. From the calculations the molecules are predicted to exist in a conformational equilibrium consisting of two non (near)-planar conformers that are identical by symmetry. Interestingly, in the internal rotation potential functions the planar conformer appears to be a stable minimum (also optimization converges to planar), however the vibrational frequencies were computed and the planar conformer exhibited an imaginary one, indicating that it is a maximum with respect to one of the internal coordinates. Only optimization without any restrictions and starting from a non (near)-planar structure converged to a real minimum with a non (near)-planar geometry. In the minimum structure, vibrational infrared and Raman spectra are calculated and those for phenylphosphonic acid are compared to experimental ones, showing satisfactory agreement. The rather low intensity of the OH bands in the experimental infrared spectrum (as compared to normal organic acids) indicates rather weak hydrogen bonding with at most dimers present. Normal coordinate calculations are carried out and potential energy distributions are calculated for the molecules in the non (near)-planar conformations providing a complete assignment of the vibrational modes to atomic motions in the molecules. From the rather low rotational barriers we conclude, in agreement with the results from the literature (for other P=O compounds) based on localized orbitals, that conjugation effects are absent - or at least negligible - as compared to electrostatic and steric ones.

By X-ray photoelectron spectroscopy (XPS), using the technique of layer-by-layer analysis, the films of (HfO₂)_x(Al₂O₃)_1-x solid solutions synthesized by chemical vapor deposition are studied. The possibility to determine the structure of solid binary solutions based on the analysis of the XPS spectra is demonstrated.

A strict approach to determine the adiabatic compressibility of a solvent at constant entropy of the solution is developed. It is shown that the apparent adiabatic compressibility of a solute is not strictly equal to the pressure derivative of the apparent molar volume of a solute at constant entropy of a solution in the general case. With this approach, the equation for hydration numbers and adiabatic compressibility of hydrate complexes is obtained thermodynamically correctly. Parameters of the hydration of potassium chloride, bromide, and iodide are found.

Cyclohexane and 2,3-dimethylbutane molecules are the most compact among saturated С6-hydrocarbons. They have a similar size and are arranged in the liquid phase like atoms in simple liquids. However, the cyclohexane density is higher approximately by 20% than that of 2,3-dimethylbutane. The reasons of this distinction are discussed. It can be explained within the concepts of the physics of simple liquids. According to them, a small variation of the radius of a particle hard core or the pair interaction energy can lead to appreciable changes in the structure and density of a liquid. The obtained results give grounds to discard the explanations based exclusively on the features of the shape of the given molecules.

The formation of solid solutions in the Re-Rh system upon thermobaric treatment (P = 4 GPa, T = 1600°C) of nanocrystalline composite mixtures containing rhodium and rhenium is studied. The boundaries of the decomposition region of solid solutions in the Re-Rh system under high pressure are found. It is shown that they coincide with the boundaries found at normal pressure.

In the Bi₂O₃-SiO₂-O₅ system, single crystal solid solutions of the sillenite family of the general composition Bi₂₄(Bi,Si,V)₂O₄₀ are obtained by a hydrothermal method and for the first time characterized by neutron and X-ray diffraction analysis. The tetrahedral position is found to contain vanadium ions with different formal charges (V⁴⁺ and V⁵⁺) responsible for green and orange colors, respectively, of the samples. For the first time, for some sillenites of this system dissymmetrization of the structure (a transition from the I23 space group into P23) is revealed, which is caused by the presence of several atoms in one crystallographic position and also by crystal growth conditions.

Crystallographic analysis is used to study the structure of (Cd,Pb)Bi₂S₄ (kudriavite), Bi₃In₅S₁₂, Pb₄In₃Bi₇S₁₈, Pb_1.6In₈Bi₄S₁₉, Pb₄In₂Bi₄S₁₃, Bi₂In₄S₉ lozenge-like sulfides (with the m plane perpendicular to the translation ~4 Å). It is shown that the structure bases contain regular cation and anion sublattices whose conjugation within the common translation cell is determined by the cation/anion ratio. The independent collective ordering of cations results in complex variants of their occupation of separate crystallographic sites. Sometimes independent anionic ordering leads to unusual coordination environments.

For the first time, new hybrid organic-inorganic layered zirconium pentafluorides of methylammonium, glycinium, and β-alanine with the composition (CH₃NH₃)ZrF₅·0.5H₂O, (H₃NCH₂COOH)ZrF₅·2H₂O, and (H₃N(CH₂)₂COOH)ZrF₅ are synthesized and their structures are analyzed. In the studied compounds, CN of the Zr atom is 8, and its coordination polyhedron represents a dodecahedron sharing its 6 vertex with three neighboring Zr polyhedra. The Zr dodecahedra are joined with each other in planar netlike anion layers of the composition . The anion layers are hydrogen bonded into a three-dimensional structure by H₂O cations and molecules.

Using the single crystal X-ray diffraction data (150 K, Bruker X8 Apex CCD autodiffractometer, МоK_α radiation), the crystal structure of the [Cd₂L₂Cl₄]·CH₂Cl₂ (L = pyrazolylquinoline, the derivative of monoterpenoid (+)-3-carene) compound is determined. Crystals are monoclinic, unit cell parameters are: a = 10.7005(4) Å, b = 16.8491(4) Å, c = 11.9658(4) Å, β = 93.308(1)°, Р2₁ space group. The structure is formed from discrete acentric molecules of a binuclear [Cd₂L₂Cl₄] complex and uncoordinated CH₂Cl₂ molecules. The Cd²⁺ ions coordinate N atoms of bidentate chelating ligands L, which leads to the closure of two five-membered chelate CdN₃C rings. The coordination sphere of Cd atoms also includes three Cl atoms (two bridging and one terminal), consequently, two CdCl₃N₂ coordination sites and a Cd₂Cl₂ metal ring are formed. The Cl₃N₂ polyhedra have the form of distorted tetragonal pyramids. The CH₂Cl₂ molecules located in the channels formed by the complexes are linked with them by weak H-bonds. The excitation spectra of L and the CdLCl₂ compound contain bands with λ_max of 352 nm and 360 nm respectively. At 300 K and λ_excit 350 nm, in the photoluminescence spectrum of L a rather intense broad split band with λ_max 372 nm and 386 nm is observed. The photoluminescence spectrum of the CdLCl₂ compound contains a broad band with λ_max 418 nm. The photoluminescence intensity of this compound is significantly lower than that of L.

For 12 acetylacetonates of the composition M(acac)_n (n = 2, 3, or 4) and M(acac)(С₂Н₄)₂ (М is a metal) the total area (⁰S) of the faces of Voronoi-Dirichlet polyhedra (VDP) corresponding to all intermolecular contacts of one molecule in the crystal structure and the total volume of pyramids (⁰V), whose bases are formed of such faces and the vertices are occupied by the nuclei of atoms participating in intermolecular contacts, are determined. The key features of non-bonded interactions are considered. The existence of a linear dependence of the sublimation enthalpy of acetylacetonates on the ⁰S or ⁰V parameters of their molecular VDP is revealed. It is shown that the sublimation enthalpy of Ga(acac)₃ requires the refinement and theoretically should be 124 kJ/mol.

Crystal structures of two modifications of a binuclear Pd₂(μ-ac)₂(acac)₂ complex are studied at 150 K and 297 K (ac = acetate; acac = acetylacetonate). It is demonstrated that in both cases, the packing of the complexes can be considered as pseudohexagonal, the molecules forming infinite chains by interactions between chelate rings with the shortest contacts Pd…C_γ ~ 3.3 Å

The structures of volatile pyridine adducts of trimethylplatinum(IV) β-diketonates derived from acetylacetone (Hacac) and dipivaloylmethane (Hdpm) are studied for the first time. Their preparation is reported and the data of thermal studies obtained by the DTA technique are presented. The structures of the compounds in question comprise monomeric complexes. The platinum atom is coordinated to three carbon atoms of methyl groups, two oxygen atoms of β-diketone, and the nitrogen atom of the pyridine molecule. The (PtC₃O₂N) coordination core has the shape of a slightly distorted octahedron. The geometrical characteristics of the coordination cores are the following: in all complexes, the values of Pt-O, Pt-C_Me,
Pt-N bond lengths and O-Pt-O chelate angles fall within 2.122-2.146 Å, 1.986-2.079 Å, 2.131-2.186 Å and 89.3-90.6° respectively.

Novel complex salts [Au(en)₂]Cl(ReO₄)₂ (I) and [Au(en)₂](ReO₄)₃ (II), en = ethylenediamine, are obtained. Their crystal structures are determined by single crystal X-ray diffraction. Complex I crystallizes in the triclinic crystal system: a = 6.2172(7) Å, b = 7.1644(8) Å, c = 8.8829(8) Å, α = 96.605(4)°, β = 110.000(4)°, γ = 97.802(4)°, Р-1 space group, Z = 1, d_x = 3.905 g/cm³; complex II crystallizes in the monoclinic crystal system: a = 15.244(2) Å, b = 7.6809(8) Å, c = 9.3476(12) Å, β = 127.004(3)°, С2 space group, Z = 4, d_x =
4.057 g/cm³.

The complex of terbium(III) with dipivaloylmethane (2,2,6,6-tetramethylheptane-3,5-dione = Htmhd) [Tb(tmhd)₃]₂ (1) and two its adducts with bipyridyl (Bipy) and phenanthroline (Tb(tmhd)₃·Bipy (2) and Tb(tmhd)₃·Phen (3)) are synthesized and analyzed by single crystal X-ray diffraction. The crystals of [Tb(tmhd)₃]₂ (1) belong to the monoclinic crystal system: P2₁/n space group, a = 12.2238(2) Å, b = 27.6369(5) Å, с = 21.8740(4) Å, β = 105.146(1)°, V = 7133.0(2) ų, Z = 4; the crystals of Tb(tmhd)₃·Bipy (2) and Tb(tmhd)₃·Phen (3) belong to the triclinic crystal system with unit cell parameters: (2) space group, a = 11.0554(6) Å, b = 12.2761(7) Å, с = 17.7096(8) Å, α = 77.457(2)°, β = 85.557(2)°, γ = 69.659(2)°, V = 2199.8(2) ų, Z = 2; (3) space group, a = 10.8814(3) Å, b = 12.2852(4) Å, с = 18.3590(6) Å, α = 80.463(1)°, β = 87.587(1)°, γ = 68.640(1)°, V = 2253.6(1) ų, Z = 2. The structures of the complexes are molecular and involve isolated [Tb₂(tmhd)₆] (1), Tb(tmhd)₃·Bipy (2), and Tb(tmhd)₃·Phen (3) molecules. The thermal properties of the obtained terbium complexes are studied by TG-DTA.

The NH₄[Eu^III(Cydta)(H₂O)₂]·4.5H₂O (I) (H₄Cydta = trans-1,2-cyclohexanediamine-N,N,N′,N′-tetraacetic acid) and K₂(pdta)₂(H₂O)₂]·6H₂O (II) (H₄pdta = propylenediamine-N,N,N′,N′-tetraacetic acid) complexes are prepared by heat-refluxing and acidity-adjusting methods respectively, and their composition and structures are determined by elemental analyses and single crystal X-ray diffraction techniques. The complex I has a mononuclear structure, crystallizes in the triclinic crystal system with the space group; the central Eu^III ion is eight-coordinated by a hexadentate Cydta ligand and two water molecules. The crystal data are as follows: a = 8.653(4), b = 10.041(4), c = 14.405(6) Å, α = 88.469(6), β = 74.892(6), γ = 88.256(7)°, V = 1207.5(9) ų, Z = 1, D_c = 1.731 g/cm³, μ = 2.669 mm^-1, F(000) = 638, R = 0.0257, and wR = 0.0667 for 3807 observed reflections with I ≥ 2σ(I). The EuN₂O₆ part in the [Eu^III(Cydta)(H₂O)₂]^- complex anion forms a pseudo-square antiprismatic polyhedron. The complex II is eight-coordinate as well; it is a binuclear structure that crystallizes in the monoclinic crystal system with the C₂/c space group; half of the central Eu^III ion is coordinated by two nitrogen atoms from one hexadentate pdta ligand and six oxygen atoms from the same pdta ligand, one water molecule and carboxylic group from the neighboring pdta ligand respectively. The crystal data are as follows: a = 19.866(3), b = 9.1017(12), c = 21.010(3) Å, β = 104.972(2)°, V = 3670.1(9) ų, Z = 8, D_c = 2.046 g/cm³, μ = 3.710 mm^-1, F(000) = 2240, R = 0.0213 and wR = 0.0460 for 4183 observed reflections with I ≥ 2σ(I). Otherwise, the two EuN₂O₆ parts in the (pdta)₂(H₂O)₂]^2- complex anion form a pseudo-square antiprismatic polyhedron.