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New coordination compounds of cobalt(II), nickel(II), and copper(II) halides with 2-(3,5-dimethylpyrazol-1-yl)benzimidazole (L) of the composition [CoLCl2] (1), CoL2Cl2 · 2H2O · EtOH (2), [NiL(H2O)4]Cl2 · H2O · EtOH (3), NiL2Cl2 · 2H2O · EtOH (4), and [CuL2Br]Br · H2O (5) were synthesized. The compounds were characterized by electronic (diffuse reflectance) spectroscopy, IR spectroscopy, and powder X-ray diffraction. The crystal structures of compounds 1, 3, and 5 were determined by single-crystal X-ray diffraction. The cytotoxic properties of the ligand and compound 5 were evaluated in the Hep-2 cell line.

Coordination compounds [Eu{Ph2P(O)Pym}2(NO3)3] (1) and [Tb{Ph2P(O)Pym}2(MeOH)(NO3)3] (2) are synthesized by the interaction of Eu(III) and Tb(III) nitrates with diphenyl(pyrimidin-2-yl)phosphine oxide (Ph2P(O)Pym). According to single crystal XRD data, the crystal structures of 1 and 2 consist of molecules of mononuclear complexes. The Ph2P(O)Pym ligand is bidentate chelating and monodentate in complexes 1 and 2 respectively; coordination polyhedra of the Ln atom are N2O8 in 1 and O9 in 2. The presence of C–H⋯O hydrogen bonds between the neighboring molecules of the complexes leads to the formation of dimeric ensembles organized in chains (in 1) and layers (in 2) by weaker hydrogen bonds. The complexes exhibit metal-centered photoluminescence in the solid state at 300 K with long lifetimes of excited states (τ > 1 ms) and luminescence quantum yields φ = 28% and 14% for complexes 1 and 2 respectively.

Chiral complexes [Ln((–)-L)2(NO3)3] (Ln = Sm (1), Eu (2), Tb (3)) with an optically active ligand (–)-L containing 1,10-phenanthroline and (–)-borneol moieties and also [Ln((±)-L)2(NO3)3]·1.5MeCN (Ln = Sm (4), Eu (5), Tb (6)) compounds with a racemic ligand (±)-L based on 1,10-phenanthroline and (+)-, (–)-borneol are synthesized. According to single crystal X-ray diffraction data, mononuclear complexes 1-3 are isostructural and crystallize in the non-centrosymmetric space group P43212. The crystal structures of isostructural complexes 4-6 crystallizing in the centrosymmetric space group C2/c contains (+)- and (–)-enantiomeric molecules of the mononuclear complex and MeCN molecules. In complexes 1-6, the (–)-L, (±)-L, and $$\text{NO}_{3}^{-}$$ ligands perform the bidentate chelate function (N4O6 coordination polyhedron of the Ln atom). Complexes 2 and 3 have high quantum yields (φ = 52% and 41%) and long-life luminescence (τ = 1.4 ms and 1.2 ms) in the solid state at 300 K. The luminescence quantum yields of chiral complexes 1-3 are found to several times exceed the quantum yields of racemic complexes 4-6.

Complex ZnLCl2·EtOH·H2O (I) where L is chiral 9,9′-bi-4,5-diazafluorenylidene containing fragments of natural monoterpenoide (–)-α-pinene is synthesized. The crystal structure of I is composed of ZnLCl2 mononuclear complex, solvate EtOH, and H2O molecules. The coordination polyhedron Cl2N2 of the Zn atom is a distorted tetrahedron. L is a bidentate cyclic ligand, involving only two N atoms in the coordination. Complex I is characterized by IR and NMR spectroscopy and its thermal properties are analyzed. In the solid phase, L exhibits photoluminescence is the visible range (λmax = 610 nm).

PdL1,2Cl2·H2O (I, II) and CuL1Cl2·H2O (III) complexes (L1 and L2 are 1-terpenyl-3-thiosemicarbazides of pinane and para-menthane series, respectively) are obtained. Single crystals of complexes I and [PdL3Cl2] (IV) (L3 is the product of hydrochlorination of ligand L2) have been grown. According to XRD data, crystal structures of I, IV consist of complex cations [PdLCl]+ and outer-sphere anions Cl−. The coordination polyhedron N2SCl is a distorted square. L1 and L3 are tridentate ligands. Free ligands L1, L2 and complexes I-III are studied using IR spectroscopy; conclusions on the structure of the Cu(II) complex are inferred from the analysis of obtained data. Cytotoxic properties of L1, complexes I and III, as well as the carboplatin pharmaceutic are studied on the Hep2 (human larynx carcinoma) cell line. Complexes I and III are shown to be moderately cytotoxic: they are twice as less toxic with respect to Hep2 cells than carboplatin that is used in the experiment as the reference complex.

Ionic complexes of the composition [LnL2(NO3)2]2[Ln(NO3)5]3Me2CO (Ln = Sm (1), Eu (2), Tb (3), Dy (4)) with an optically active ligand L containing 1,10-phenanthroline and (+)−3-carene moieties are synthesized. According to the X-ray crystallographic data, the crystal structure of compound 2 is composed of complex [EuL2(NO3)2]+ cations (N6O4 polyhedron) and complex [Eu(NO3)5]2− anions (O10 polyhedron), and also Me2CO molecules. The L and NO3 ligands perform both tridentate and bidentate chelating functions respectively. Complexes 1–4 are isostructural and crystallize in the non-centrosymmetric space group P1; their magnetic properties are studied in the temperature range 2–300 K. The μeff values for 1–4 at 300 K are 3.14 μB, 6.08 μB, 16.76 μB, and 18.30 μB respectively and are typical of Ln3+ ions. For complex 3 significant anisotropy results in a nonlinear field dependence of the magnetization at 2 K. Complexes 1–4 exhibit metal-centered orange (Sm3+), red (Eu3+), green (Tb3+), and yellow (Dy3+) luminescence in the solid state at room temperature. Luminescence quantum yield decreases for solid samples in the order 2 > 1 > 3 ≈ 4.

Complexes [Zn(L)Cl2] (I), Cu(L)Cl2 ∙ H2O (II), Zn(L1)Cl2 ∙ 0.5H2O (III), and Cu(L1)Cl2 ∙ 0.5H2O (IV) (where L and L1 are the diaminopropylene and diaminoethylene derivatives of deoxycholic acid, respectively) are synthesized. The structure of mononuclear complex I is determined by X-ray structure analysis (CIF file CCDC no. 1875305). The coordination polyhedron of the Zn atom (Cl2N2) is a distorted tetrahedron. According to the X-ray diffraction data, the crystals of compounds III and IV are isostructural. It is shown by IR spectroscopy that the structures of complexes II–IV are similar to that of complex I. In the solid phase, compounds L and L1 possess photoluminescence in the visible spectral range (λmax = 440 and 415 nm, respectively). Complex formation with Zn2+ ions does not change the photoluminescence properties of L and L1.

Zinc(II) complexes with 1,10-phenanthroline and tetrafluoroterephthalate and octafluorobiphenyl 4,4′-dicarboxylate anions have been synthesized. According to the IR spectral data, the complexation involves coordination of the metal ion to the nitrogen atoms of phenanthroline and carboxylate oxygen atom of the acid anion. The complexes show photoluminescence in the visible region of the spectrum. The structure of the complex salt [Zn(H2O)6][Zn(H2O)4(L2)2] · H2O, where L2 is octafluorobiphenyl-4,4′-dicarboxylate anion (monodentate ligand), has been determined by X-ray analysis.

The complex salt {[CuL2][Cu4I6]•MeCN}n (1) and the compound [Cu4L3I4]•3 MeCN (2) (L is a chiral ligand bearing a natural monoterpene (+)-3-carene moiety) were synthesized. The crystal structures of compounds 1 and 2 were determined by X-ray diffraction. The structure of compound 1 consists of complex cations [CuL2]2+ (N3O2 polyhedron is a trigonal bipyramid) and CuI coordination polymers (CuI4 polyhedron is a tetrahedron) as anions. The experimental magnetic moment μeff at 300 K is 1.90 μB, which is consistent with the X-ray diffraction data and the assumption that compound 1 is mixed-valence. The structure of compound 2 comprises a tetranuclear CuI complex, in which three Cu atoms are coordinated by two N atoms of the ligand L and two I atoms, and the fourth Cu atom is coordinated by four I atoms (coordination polyhedra are distorted tetrahedra). Compounds L and 2 were found to influence the viability of human laryngeal carcinoma cells (Hep2). The IC50 value for complex 2 (13.0±1.7 μM) is substantially smaller than IC50 for compound L (30.5±0.5 μM).

Complexes [CuL1Cl2] (I), [CuL2Cl2] · EtOH (II), and Cu2L3Cl4 (III) containing esters of the N-derivatives of optically active amino acids based on (+)-3-carene (L1, L2) and (‒)-α-pinene (L3) are synthesized. The crystal and molecular structures of compounds I and II are determined by X-ray diffraction analyses (CIF files CCDC nos. 1560071 (I), 1560072 (II)). The crystal structure of compound I consists of mononuclear complex molecules. In the structure of compound II, the unit cell contains two crystallographically independent molecules of mononuclear complex [CuL2Cl2] and two EtOH molecules. Ligands L1 and L2 perform the tridentate-chelating function by the N atoms of the NH and NOH groups and by the O atom of the C=O group. In compounds I and II, the coordination polyhedra Cl2N2O of the Cu atoms are trigonal bipyramid. According to the data of IR and electronic spectroscopy, binuclear complex III has similar coordination polyhedra. The experimental values of μeff for compounds I, II, and III at 300 K are 1.93, 1.88, and 2.71 μB. For complex III, the μeff(T) dependence in a range of 2–300 K indicates a weak ferromagnetic exchange interaction.

CuLCl, CuL1Cl, PdLCl2, and PdL1Cl2 complexes [L and L1 being (+)-camphor and (–)-carvone thiosemicarbazones, respectively] have been synthesized. The structure of binuclear [Pd2L22Cl4] complex has been determined by means of X-ray diffraction. The L2 ligand (dehydrogenated (–)-carvone thiosemicarbazone) is coordinated via the bridging S atom to two Pd atoms. The complexes of Cu(I) and Pd(II) presumably have polynuclear and binuclear structure, respectively. These facts are in good agreement with IR and NMR spectroscopy as well as mass spectrometry data which indicate the coordination of L and L1 ligands via the S atom. The influence of L1 and PdL1Cl2 on viability of the Hep2 cell line has been studied. The PdL1Cl2 complex is more cytotoxic than L1 ligand.

Complexes ZnLCl2 (I) and [CdLCl2] n (IV), where L is chiral bis-pyridine containing fragments of natural monoterpenoide (–)-α-pinene are synthesized. Single crystals of [ZnLCl2]·CH2Cl2 (II), [ZnLCl2]·i-PrOH (III), and IV compounds are grown. The crystal structures of II and III are composed of mononuclear ZnLCl2 complex molecules and solvate CH2Cl2 and i-PrOH molecules; the coordination polyhedron of the zinc atom Cl2N2 is a distorted tetrahedron. According to the single crystal XRD data, complex IV is a 1D coordination polymer; the coordination core CdN2Cl4 is a distorted octahedron and Cl atoms are bridging ligands. In the structures of II, III, and IV the L molecule functions as a bidentate chelate ligand. In the solid phase, complexes I and IV exhibit photoluminescence in the visible range (λmax 505 nm and 460 nm respectively). The band intensity in the photoluminescence spectra of I and IV complexes considerably exceeds the band intensity in the spectrum of free L.

Complexes Pd(LH)Cl2 (LH is the N-derivative of β-alanine based on (–)-α-pinene) and PdLEtCl2 (LEt is ethyl ester of LH) are synthesized. The X-ray diffraction analysis (СIF file ССDC no. 1471432) shows that the single crystals of the [PdLEtCl2] complex belong to the racemate. The crystal structure contains (+)- and (–)-enantiomeric molecules of the mononuclear complex. Ligand LEt is bidentate chelating. The coordination PdCl2N2 core is a distorted square. The contacts Pd…Cl and hydrogen bonds N–H…Cl between molecules of the (+)- and (–)-enantiomers result in the formation of dimeric ensembles, which are joined into chains due to the C–H…Cl hydrogen bonds. According to the X-ray powder diffraction data, the products of the synthesis of complex [PdLEtCl2] contain both the racemate and (+)-enantiomer. The (+)-enantiomer is isolated by the recrystallization of the synthesis product. Complex Pd(LH)Cl2 is an optically active right-handed compound. According to the NMR data, complex PdLEtCl2 does not dissociate in a CDCl3 solution. The results of IR and NMR spectroscopy indicate that the molecular structure of complex Pd(LH)Cl2 is similar to that of [PdLEtCl2].

Complexes (A)[Gd(L)4] and [Gd(Phen)(L)3] (L = iso-Bu2PS2-, C4H8NCS2-; A = NH4+, Et4N+) are synthesized. The crystal structure of compound [Gd(Phen)(iso-Bu2PS2)3] · MeCN is determined by X-ray diffraction analysis (CIF file CCDC no. 1455418). The structure consists of molecules of the mononuclear complex [Gd(Phen)(iso-Bu2PS2)3] and MeCN. The coordination polyhedron N2S6 of the Gd atom is a distorted antiprism. The complexes exhibit phosphorescence in a range of 400–600 nm. The energies of the triplet levels of the ligands C4H8NCS2-(23336 cm–1) and iso-Bu2PS2-(23506 cm–1) are determined from the phosphorescence spectra of complexes (A)[Gd(L)4] in frozen ethanol (77 K).

The detailed comparative study is carried out for crystal structure packings of the following gold(III) complexes with unsaturated ligands: [Au(C14H22N4)]Br (I), [Au(C14H23N4)](ClO4)2 (II), [Au(C14H24N4)](H3O)(ClO4)4 (III). The determining role in the topological pattern of packings I–III belongs to the compositions and structures of the cations along with the ability of the ions of the complexes to act as donors and acceptors of hydrogen bonds. The 3D packings of complexes I and II containing iminate six-membered rings are determined and stabilized by a wide network of weak hydrogen bonds (C–H…π, C–H…Au, and C–H…Br(O)) and short contacts Au(N)…O (in structure II). The structure of imine complex III is characterized by one-dimensional piles formed due to hydrogen bonds O(w)–H…O and contacts Au…O of the О(2) atom of anion Сl(1)О4- with cations (H3O)+ and [Au(C14H24N4)]3+ (CIF files CCDC 251258 (I), 276132 (II), and 287784 (III)).

Acyclic tetraazametal gold(III) perrhenate complex [Au(C9H19N4)](ReO4)2 is synthesized. The 3D crystal structure of the complex is stabilized by weak secondary interactions (N–H…O, C–H…O, С–H…Au hydrogen bonds, and Au…O contacts). The translation sublattice method shows that the motif of the mutual arrangement of cations can be considered to be pseudohexagonal. The product of the thermal decomposition of [Au(C9H19N4)](ReO4)2 in a hydrogen atmosphere is a mixture of nanocrystalline phases (HCP phases based on Re and Au) with the coherent scattering region of 24 nm and 34 nm, respectively.

The complexes [Cu(HL)Cl] · 0.25H2O (I), [Cu(HL1)Cl] · 0.5H2O (II), [Ag(HL)] · 0.5H2O (III) were obtained; HL– and (HL1)– are the anions of the chiral N-substituted aminoacetic acid derivatives containing the natural monoterpenes (+)-3-carene and (–)-α-pinene, respectively. The µeff values for paramagnetic complexes I and II are 1.92 and 1.81 µB, respectively. Single crystals of the coordination 1D polymer [Cu(HL)Cl · 2H2O]n (IV) were grown. According to the X-ray diffraction data (CIF file CCDC No. 1035219), the crystal structure of complex IV is made up of the zigzag chains [Cu(HL)Cl]n and water molecules. The coordination polyhedron of the Cu atom is a distorted square pyramid (ClN2O2). The anion HL– acts as a chelating and bridging tetradentate ligand coordinated through the N atoms of the NH and NOH groups as well as through the O atoms of the COO–groups linking two adjacent Cu atoms together. The IR spectra of complexes I and II also provide evidence for the coordination of the functional COO–, NOH, and NH groups. In complex III, the coordination sphere of the Ag atom is made up of the O atoms of the COO–group. Complex III shows weak green photoluminescence (λmax = 530 nm).

The complex of the composition [Pd2(H2L1)Cl4] (I) (H2L1 is a chiral bis-α-sulfanyl oxime, a derivative of natural monoterpenoid (+)-3-carene) is synthesized. Single crystals of I and solvate [Pd2(H2L1)Cl4]•0.5CH2Cl2 (II) are grown. According to the X-ray crystallographic data, the crystal structure of I consists of acentric molecules of the binuclear [Pd2(H2L1)Cl4] complex. The structure of solvate II consists of the molecules of binuclear complex I and CH2Cl2 molecules. The PdCl2NS coordination sites are distorted squares (trapezia). In the structures of I and II, the PdCl2 fragments are in the transoid position. In I, the Cl2NS planes of the two coordination sites are nearly parallel (the angle between the planes is 7.7(1)°). The similar angle in solvate II is 22.0(1)°.

Perrhenate of the tetraazamacrocyclic complex of gold(III) [Au(C14H22N4)]ReO4 is synthesized. The crystal structure of the compound is determined by single crystal X-ray diffraction. The crystallographic data are as follows: а = 7.733(2) A, b = 11.368(2) A, c = 11.685(2) A, α = 116.23°, β = 104.26°, γ = 94.96°; V = 870.3(3) A3, space group P(–1), Z = 2, dcalc = 2.647 g/cm3, R = 0.0245. The packing of the complex is comprised of double stacks of cations and chains of anions linked into two-dimensional layers due to weak intermolecular interactions (non-classical hydrogen bonds C–H…O, C–H…Au, C–H…π and the Au…Au contacts). The thermal decomposition of the obtained compound in the hydrogen atmosphere is studied. According to the powder X-ray diffraction data, the product of the reduction of the synthesized salt is a mixture of nanocrystalline phases of Re and Au with the coherent-scattering regions of 17 nm and 13 nm respectively.

The complex Pd(HL)Cl2 (I) was obtained (HL is the anthracene-containing chiral α-amino oxime derived from the natural monoterpenoid (+)-3-carene). Single crystals of its solvate [Pd(HL)Cl2] · 0.33EtOH (II) were grown. According to X-ray diffraction data (CIF file CCDC no. 1008947), the crystals are built from mononuclear molecules of complex I and uncoordinated EtOH molecules. The coordination environment of the Pd atom in complex I (PdCl2N2) makes up a distorted square (trapezoid). The compound HL acts as a chelating bidentate ligand. The [Pd(HL)Cl2] and EtOH molecules are united into chains through weak hydrogen bonds. The photoluminescence (PL) of HL and the system ZnCl2-HL in acetonitrile was studied. The emission spectra show three bands at 394, 415, and 440 nm. The photoluminescence of the system ZnCl2-HL in solution is more intense than that of HL. A study of the system ZnCl2-HL by the molar ratio method in conjunction with emission spectroscopy suggests the formation of the complex Zn(HL)Cl2 in acetonitrile.

Five compounds of the composition Ln(2,2′-Bipy)(C4H8NCS2)3 · 0.5CH2Cl2 (Ln = Sm (I), Eu (II), Tb (III), Dy (IV), and Tm (V); 2,2′-Bipy = 2,2′-bipyridine) are synthesized. According to the X-ray diffraction data (CIF file CCDC 986259), the crystal structure of compound I consists of molecules of the mononuclear complex [Sm(2,2′-Bipy)(C4H8NCS2)3] and solvate molecules CH2Cl2 (2 : 1). The coordination polyhedron N2S6 of the Sm atom is a distorted tetragonal antiprism. The X-ray diffraction analysis shows that compounds I–V are isostructural. The magnetic properties of compounds I–V are analyzed in the temperature range from 2 to 300 K. At 300 K compounds I and III are photoluminescent in the visible spectral range. The photoluminescence intensity of compound I considerably exceeds that of complex III.

The [ZnLCl2] (1) and Cd2L2Cl4 (2) complexes, where L is ethyl 2-methyl-5-(prop-1-en-2-yl)pyrido[2,3-a]phenazine-3-carboxylate, were synthesized. The complexes were characterized by elemental analyses, 1H and 13C NMR spectroscopy, and X-ray powder diffraction. Single crystals of 1 and [Cd2L2Cl4]·4CH2Cl2 (3) have been grown. The structure of 1 consists of mononuclear molecules, while the structure of 3 is built up of centrosymmetrical binuclear [Cd2L2Cl4] complex molecules and uncoordinated CH2Cl2 molecules. In 1 and 3, L acts as a bidentate chelating ligand. There is five-membered ZnN2C2 chelate cycle in the [ZnLCl2] molecule. There are two five-membered CdN2C2 chelate cycles and a Cd2Cl2 dinuclear unit in the molecule of [Cd2L2Cl4]. The coordination polyhedra are distorted tetrahedron Cl2N2 (in the structure 1) and distorted tetragonal pyramid Cl3N2 (in the structure of 3). According to IR-spectroscopic data, complex 2 is binuclear. Complexes 1 and 2 display bright luminescence in CHCl3 solutions (λmax = 477 and 475 nm, respectively) and in the solid state (λmax = 510 and 529 nm, respectively). The free L ligand shows weak luminescence intensity (λmax = 441 and 467 nm in CHCl3 and solid state, respectively).

A heteroligand complex [Sm(Biq)(iso-Bu2PS2)3]n (Biq = 6,6′-biquinoline) is synthesized. According to the X-ray diffraction data, the complex is one-dimensional coordination polymer. The crystal structure is built of chains consisting of fragments Sm(iso-Bu2PS2)3 and molecules of the bidentate-bridging ligand Biq. The coordination polyhedron N2S6 of the Sm atom is a distorted tetragonal antiprism. The complex exhibits red photoluminescence (λmax = 562, 598, 642, and 703 nm).

It is found that diffraction patterns of complexes I–V of the composition [Ln(Phen)(C4H8NCS2)3] (Ln = Sm, Eu, Tb, Dy, and Tm respectively) are similar. Single crystals of [Dy(Phen)(C4H8NCS2)3]·3CH2Cl2 (VI) obtained are. According to the X-ray crystallographic data, in the structure of VI the unit cell contains two crystallographically independent molecules of the [Dy(Phen)(C4H8NCS2)3] complex and six CH2Cl2 molecules. The N2S6 coordination polyhedron of the Dy atom is a distorted square antiprism. In the range of 2–300 K the magnetic properties of complexes I–V are studied. It is found that complex III passes to the magnetically ordered state; the spontaneous magnetization at 2 K is 24 600 G·cm3/mol. At 300 K compounds I–IV exhibit photoluminescence in the visible spectral range. It is found that the photoluminescence intensity of complex I is several times higher than the photoluminescence intensity of complexes II–IV.

3-(2-Methoxyphenylamino)caran-4-one and 2-(2-methoxyphenylamino)pinan-3-one E-oximes obtained from appropriate natural terpenes were transformed into 1: 1 complexes with PdCl2. The structures of the complexes were examined by X-ray diffraction.

Heteroligand complexes Tm(L)(iso-Bu2PS2)2(NO3) (L = 2,2′-Bipy (II), Phen (III)) are synthesized. According to the X-ray phase analysis data, complex III is isostructural to mononuclear compound [Dy(Phen)(iso-Bu2PS2)2(NO3)] including, according to the X-ray diffraction data, a coordination polyhedron DyN2O2S4 (distorted dodecahedron). Single crystals of compounds [Ln(2,2′-Bipy)(iso-Bu2PS2)2(NO3)] · C6H6 (Ln = Tm (IV), Tb (V)) are obtained. An X-ray diffraction analysis shows that the crystal structures of these isostructural compounds are formed by molecules of mononuclear complexes [Ln(2,2′-Bipy)(iso-Bu2PS2)2(NO3) and uncoordinated C6H6 molecules. In complexes IV and V, the ligands [Ln(2,2′-Bipy)(iso-Bu2PS 2 − , and NO 3 − are bidentate-cyclic. The coordination polyhedron LnN2O2S4 is a distorted dodecahedron. Complexes II and III possess photoluminescence in the visible spectral range (λmax = 478 and 477 nm, respectively).

The optically active complexes [Zn(L)2Cl2] (I) and [Zn(L1)2Cl2] (II) (L and L1 are thiosemicar-bazones of (+)-camphor and (−)-carvone, respectively) were obtained. The crystal structures of L and complex I were determined by X-ray diffraction. The structure of L consists of hydrogen-bonded molecules united into chains. The crystal structure of complex I is built from mononuclear molecules. The coordination polyhedron of the Zn atom is a distorted tetrahedron Cl2S2. The molecule L functions as a monodentate ligand. According to data from IR spectroscopy, complex II is structurally similar to complex I.

The packings of the crystal structures of the gold(III) iodide, perchlorate, and hexafluorophosphate complexes with the iminate-amine ligand, [Au(C9H19N4)]Y2 (Y = I (I), ClO4 (II), and PF6 (III)), are studied in comparison. The packings of structures I–III are similar. They are determined and stabilized by a vast network of intermolecular interactions (hydrogen bonds N-H…A, C-H…A, C-H…Au, and C-H…π and short contacts Au…A (A = I, O, F)). Structures I–III are characterized by cation-cationic and cationanionic infinite chains and closed rings formed by classical and nonclassical hydrogen bonds and contacts. The structures include multicentered hydrogen bonds. The replacement of the anion does not basically change the packing structures.

Coordination compounds Pd2(H2L2)Cl4 (I), Cu2(H2L2)Cl4 (II), Pd2(H2L3)Cl4 (III), and Cu2(H2L3)Cl4 (IV), where H2L2 and H2L3 are chiral bis-α-aminooxime ligands consisting of (+)-3-carene or (+)-limonene fragments and 4,4′-methylenedianiline linker, were synthesized and examined by NMR, ESR, and IR spectroscopy. The structure of [Cu(i-PrOH)CL2(μ-H2L3)CuCL2·H2O] (V) was determined by X-ray analysis.

The photoluminescence spectra of the known complexes, Sm(L)2(NO3)3 (I, II), Sm(L)(iso-Bu2PS2)3 (III, IV), Sm(L)(iso-Bu2PS2)2(NO3) (V, VI) (L = Phen, 2,2′-Bipy), and Sm(Phen)(C4H8NCS2)3 (VIII), and new compounds, Sm(Phen)((iso-PrO)2PS2)3 (VII), Sm(2,2′-Bipy)(C4H8NCS2)3 · 0.5CH2Cl2 (IX), are obtained and interpreted. Using the X-ray structure analysis data, the crystal structure of the [Sm(2,2′-Bipy)2(NO3)3] complex (II) is determined. Structure II consists of discrete mononuclear molecules having a ten-vertex coordination polyhedron N4O6. The ligands 2,2′-Bipy and NO 3 − are bidentate-cyclic. The influence of the composition of the complexes on the photoluminescence (PL) intensity in the series I–VI is considered. The dependence of the intensity of the band with λmax = 647 nm in the PL spectra of complexes III, VII, and VIII on the type of the sulfur-containing ligand in their composition is established. The band intensity changes in the series VIII > III > VII.

Compounds p-HOOCC6F4COOH · H2O (H2L · H2O), [Tb2(H2O)4(L)3 · 2H2O] n (I), and Tb2(Phen)2(L)3 · 2H2O (II) are synthesized. According to the X-ray structure analysis data, the crystal structure of H2L · H2O is built of centrosymmetric molecules H2L and molecules of water of crystallization. The crystal structure of compound I is built of layers of coordination 2D polymer [Tb2(H2O)4(L)3] n and molecules of water of crystallization. The ligands are the L2− anions performing both the tetradentate bridging and pentadentate bridging-chelating functions. The coordination polyhedron TbO9 is a distorted three-capped trigonal prism. Acid H2L manifests photoluminescence in the UV region (λmax = 368 nm). Compounds I and II have the green luminescence characteristic of the Tb3+ ions, and the band with λmax = 545 nm (transition 5 D 4→ 7 F 5) is maximum in intensity. The photoluminescence intensity of compound II is higher than that for compound I.

Heteroligand complexes Ln(L)(iso-Bu2PS2)2(NO3) (Ln = Sm, Tb, Dy; L = Phen, 2,2′-Bipy) (I–VI) are synthesized. The structure of Dy(Phen)(iso-Bu2PS2)2(NO3) (III) is determined from the data of X-ray structure analysis. The crystal structure of complex III is based on discrete mononuclear molecules in which the Dy atom has distorted dodecahedral coordination (polyhedron N2O2S4). The ligands Phen, iso-Bu2PS 2 − and NO 3 − are bidentate-cyclic. According to the X-ray diffraction analysis data, complexes I and II are isostructural to compound III. Complexes I–VI have photoluminescence in the visible spectral range. The photoluminescence spectra of solid samples of compounds I–VI exhibit bands corresponding to the radiative electron transitions of the Sm3+, Tb3+, and Dy3+ ions. Among the studied compounds I–VI, the Tb(III) complexes are characterized by the most intense photoluminescence.

The crystal structure of a solvate [Zn(HL)Cl]·EtOH is determined by single crystal X-ray crystallography (150 K, Bruker X8 Apex CCD autodiffractometer, MoK α radiation). The crystals are triclinic, unit cell parameters are: a = 7.4755(4) A, b = 13.9701(11) A, c = 14.4593(19) A, α = 82.277(2)°, β = 75.410(2)°, γ = 75.356(1)°, space group P1. The structure of the solvate contains two crystallographically independent complex [Zn(HL)Cl] molecules and two non-coordinated ethanol molecules. In each of the molecules, Zn2+ ions coordinate N atoms of tetradentate chelating ligands HL− and a Cl atom. ClN4 polyhedra have a distorted tetragonal pyramidal geometry. EtOH molecules make H-bonds with the complex molecules, thus facilitating the formation of chains along the x axis.

The subsolidus region of the ternary salt system Tl2MoO4-Fe2(MoO4)3-Hf(MoO4)2 was studied by X-ray powder diffraction. New compounds Tl5FeHf(MoO4)6 (5: 1: 2) and Tl(Fe,Hf0.5)(MoO4)3 (1: 1: 1). were found to be formed in this system. Crystals of new ternary molybdate of the composition Tl(FeHf0.5)(MoO4)3 were grown by spontaneous flux crystallization. Its composition and crystal structure were refined based on X-ray diffraction data. The mixed three-dimensional framework of the crystal structure is composed of Mo tetrahedra sharing O vertices with (Fe,Hf)O6 octahedra. The thallium atoms occupy wide channels in the framework.

The acyclic iminate amine gold(III) complex iodide [Au(C9H19N4)]I2 (I) was obtained. The crystal structure of complex I is stabilized by weak secondary interactions N-H…I, C-H…Y (Y = I, Au, and π), and Au…I forming an infinite 2D network. Double stacks of cations along the axis x are united through zigzag chains of H-bonds and of secondary contacts. Structure I contains 3–14-membered cation-cation and cation-anion rings. The anions I(1)− and I(2)− act as bridges in structure I.

The thermal decomposition of the chelate Cd(n-BuOCS2)2 (I) in EtOH and DMF, either in the absence or in the presence of Ph3P, yields finely disperse CdS particles. Mixed-ligand complex Cd(Ph3P)(n-BuOCS2)2 (II) has been synthesized. Cd(Ph3P)(n-BuOCS2)2 · Ph3P (III) single crystals have been grown. By X-ray crystallography, the crystal structure of III is built of [Cd(Ph3P)(n-BuOCS2)2] mononuclear complex molecules and uncoordinated Ph3P molecules, which reside inside channels formed by complex II molecules. The coordination polyhedron around a Cd atom is a tetragonal pyramid where the base is formed by the four S atoms of the two bidentate chelating ligands n-BuOCS2− and the P atom of the Ph3P ligand is at the axial vertex. In the structure of III, there are supramolecular assemblies of two complex II molecules.

A ternary salt system Rb2MoO4-Ce2(MoO4)3-Zr(MoO4)2 is studied by powder XRD. Single crystals of 5:1:2 ternary rubidium-cerium-zirconium molybdate Rb5CeZr(MoO4)6 are obtained by solution melt crystallization under spontaneous nucleation conditions. The crystal structure is solved by X-ray crystallography (X8 APEX automated diffractometer, MoK α radiation, 1274 F(hkl), R = 0.0456). The parameters of a trigonal unit cell are: a = b = 10.7248(2) A, c = 38.796(1) A, V = 3864.52(14) A3, Z = 6, $R\bar 3c$ space group. The three-dimensional complex framework comprises Mo tetrahedra linked to two independent (Ce,Zr)O6 octahedra. Two types of rubidium atoms occupy large cavities of the framework.

Chiral sodium salts of N-derivatives of aminoacetic acid based on (+)-3-carene (HLNa) and (−)-α-pinene (HLNa) were synthesized. Complexes Zn(HL)Cl (1), Cd(HL)Cl·0.5H2O (3), Zn(HL′)Cl·0.5H2O (4), and Cd(HL′)Cl·0.5H2O (5) were obtained. The single crystals of the coordination polymer [Zn(HL)Cl·2H2O]n (2) were grown. According to the X-ray diffraction analysis, the crystal structure of 2 consists of 1D chains built of Zn(HL)Cl and water molecules. The coordination polyhedron ClN2O2 is a distorted square pyramid. The HL− ligand performs the chelating tetradentate-bridging function, and the COO− group binds two adjacent Zn atoms. The IR spectroscopy data for compounds 1 and 3–5 indicate the coordination of the COO−, NOH, and NH functional groups. The excitation and photoluminescence (PLM) spectra of the solid samples of compounds HLNa, HL’Na, 1, and 3–5 were recorded at room temperature. The compounds exhibit blue PLM. The intensity of PLM of the CdII complexes is higher than that of the ZnII complexes, which is a characteristic feature of PLM of the studied compounds.

Using the single crystal X-ray diffraction data (150 K, Bruker X8 Apex CCD autodiffractometer, MoK 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) A, b = 16.8491(4) A, c = 11.9658(4) A, β = 93.308(1)°, P21 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 λmax of 352 nm and 360 nm respectively. At 300 K and λexcit 350 nm, in the photoluminescence spectrum of L a rather intense broad split band with λmax 372 nm and 386 nm is observed. The photoluminescence spectrum of the CdLCl2 compound contains a broad band with λmax 418 nm. The photoluminescence intensity of this compound is significantly lower than that of L.

The crystal structure of the complex (N2H5)[Ni(NH2NHCOO)3] · H2O (I) was refined using X-ray diffraction data (obtained on an Apex X8 diffractometer, MoKα radiation, 1830 Fhkl, R = 0.0182). The structure is built of complex anions [Ni(NH2NHCOO)3]−, cations N2H5+, and water molecules and is characterized by strong hydrogen bonds N-H…O, O-H…O, and N-H…N. The N3O3 coordination polyhedron around a Ni atom is a slightly distorted octahedron. The thermal decomposition of complex I was studied in high-boiling organic liquids. The feasibility of preparing non-pyrophoric nickel powders having particle sizes of up to 20 nm is shown.

3,5-Dimethyl-1H-pyrazolide of 3-O-acetyl ursolic acid (II) is obtained in the course of the interaction of 3 O-acetyl ursolic acid acyl chloride (I) and 3,5-dimethyl-1H-pyrazole. The crystal structure of compound II is determined from the single crystal XRD data (150 K, Bruker X8 Apex CCD autodiffractometer, MoKα radiation). The crystals are rhombic, the unit cell parameters are as follows: a = 10.6034(2) A, b = 12.4096(2)A, c = 24.5972(5)A, P212121 space group. The structure consists of discrete acentric molecules. When pyrazolide II is boiled in the alcohol alkali solution, secondary hydroxyl is deacetylated and 3,5-dimethyl-1H-pyrazolide of ursolic acid IV is formed. Compounds II and IV are studied by NMR spectroscopy.

The complex [Au(C14H22N4)][AuBr2] with two types of gold atoms (Au(III) and Au(I)) was obtained. In the cation 5,7,12,14-tetramethyl-1,4,8,11-tetraazacyclotetradeca-4,6,11,13-tetraenatogold(III), the Au atom is coordinated by four N atoms of the tetraazamacrocyclic amide ligand to make up a distorted square. The dibromoaurite(I) anion is linear. The conformation and packing of the structure is determined and stabilized by weak intermolecular hydrogen bonds C-H…Br and C-H…Au, an aurophilic interaction Au(I)…Au(III), and coordination bonds Au…N.

The following chiral compounds were synthesized: [ZnLCl2] · EtOH (I) and ZnLCl2 (II), where L is the pyrazolin-5-ol derivative obtained from terpene (+)-3-carene. According to the X-ray diffraction data, the crystal structure of compound I is built of acentric molecules of the mononuclear ZnLCl2 complex and EtOH molecules. In molecules of the complex, the Zn2+ ion is coordinated by two N atoms of the bidentate chelating ligand L and two Cl atoms at the vertices of the distorted tetrahedron. The intermolecular contacts and the hydrogen bonds Cl(1)…H-O(1) between the adjacent ZnLCl2 molecules result in the formation of chains parallel to the y axis. The reactant L and solvate I possess weak photoluminescence in the visible spectral range. Complex II exhibits more intense photoluminescence at λmax = 416 and 517 nm.

It is revealed that at 300 K Sm(Phen)(i-Bu2PS2)3 (I) and Sm(2,2′-Bipy)(i-Bu2PS2)3 (II) complexes have photoluminescence properties typical of the Sm3+ ion. In the spectra, three bands are observed with 7nmax = 564 nm, 600 nm, and 645 nm. Single crystals of Sm(Phen)(i-Bu2PS2)3·MeCN (III) are grown, and the structure of the compound is determined based on the X-ray diffraction data (X8 Apex diffractometer, MoK6h radiation, 7685 F hkl, R = 0.0258). Crystals of III are triclinic, unit cell parameters are a = 11.0554(3) A, b = 15.0446(3)A, c= 15.4849(4)A; 6h = 89.218(1)°, β = 75.555(1)°, γ = 73.484(1)°, V= 2386.6(1)A3, Z=2, ρcalc = 1.391 g/cm3, P1 space group. The structure of III is formed from the molecules of mononuclear complex I and MeCN molecules. A coordination polyhedron of the Sm atom is an N2S6 tetragonal antiprism. It is shown that the structure of III includes dimeric assemblies of the molecules of complex I.

The dinuclear gold(III) complex, [Au2(HL)(L)2](ClO4)3(OH) (I) (HL = 1,3-diaminopropane), with two amide bridges has been synthesized for the first time. According to the X-ray diffraction data, the crystal structure of complex I consists of the complex cations [Au2(HL)(L)2]4+ and anions ClO4− and OH−. The coordination sites AuN4 are insignificantly distorted squares. In the four-membered ring Au2N2, the gold atoms are bound by the bridging nitrogen atoms of the deprotonated primary amine.

The chiral complexes [PdL1Cl2] (I) and [PdL2Cl2] (II) (where L1 and L2 are hydroxypyrazolylquinoline and pyrazolylquinoline, respectively, based on the monoterpenoid (+)-3-carene) were obtained and examined using X-ray diffraction. The crystal structures of complexes I and II are built from mononuclear acentric molecules. The Pd2+ ions coordinate two N atoms of the chelating bidentate ligand L1 or L2 and two Cl atoms. The coordination polyhedron Cl2N2 is a square distorted in a tetrahedral manner. In structure I, adjacent molecules are linked by intermolecular contacts and hydrogen bonds Cl···H-O, which gives rise to chains aligned with the axis x. In structure II, contacts that are substantially shorter than the van der Waals interactions were not detected.

Paramagnetic Cu(HL)Cl2 · 0.25CHCl3 (I) and Cu(HL)C12 · 0.25CH2C12 (II), where HL is the optically active morpholino oxime obtained from the terpenoid caryophyllene, were synthesized. The crystals of Cu(HL)Cl2 · CHCl3 (III) were isolated. According to X-ray diffraction data, the crystals of III are composed of acentric mononuclear complex molecules Cu(HL)Cl2 and solvate molecules CHCl3. In the complex molecules, the Cu ion coordinates two N atoms of the bidentate chelating ligand HL and two C1 atoms at the vertices of a distorted tetrahedron. The translationally identical molecules of the complex combined by H-bonds form chains along the axis x.

A compound with the composition Nd(C6F5COO)3· H2O (I) is prepared. Single crystals are grown, and their single crystal XRD analysis of the Nd2(H2O)8(C6F5COO)6]·2H2O (II) compound is performed. The crystals are triclinic: a = 7.693(2) A, b = 9.394(2) A, c = 18.203(4) A, α = 81.91(3)°, β = 84.41(3)°, γ = 88.97(3)°, Z = 1, dx = 2.223 g/cm3. The structure is composed of symmetrical molecules of the binuclear [Nd2(H2O)8(C6F5COO)6] complex and crystallization water molecules. The C6F5COO- ligands are monodentate and tridentate bridging- chelating, which results in a closure of two four-membered chelate cycles NdO2C and a four-membered metal cycle Nd2O2. The NdO9 polyhedron is a distorted one-capped tetragonal antiprism.