The crystal structures of two new palladium complexes with 4-methylamino-3-penten-2-one CH3C(NHCH3)CHC(O)CH3 (Hmki) are determined. The crystals β-trans-Pd(mki)2 (1) and Pd(ki) (mki)·0.5(C6H6) (2) (ki = CH3C(NH)CHC(O)CH3, mki = CH3C(NCH3)CHC(O)CH3). The crystals belong to the triclinic system with the following unit cell parameters for 1: space group P1̅ , a = 7.1877(3) Å , b = 7.2668(4) Å, c = 7.3246(3) Å, α = 83.903(1)°, β = 61.263(1)°, γ = 74.197(1)°, V = 322.64(3) Å3, Z = 1; for 2: space group P1̅ , a = 7.1787(2) Å, b = 9.4578(4) Å, c = 12.1817(7) Å, α = 108.361(1)°, β = 96.160(1)°, γ = 107.046(1)°, V = 732.09(6) Å3, Z = 2. The complexes have molecular structures composed of isolated Pd(mki)2 and Pd(ki)(mki) molecules in 1 and 2 respectively. The electron density distribution in α-trans-Pd(mki)2, β-trans-Pd(mki)2 (1) and mixed-ligand Pd(ki)(mki)·0.5(C6H6) (2) complexes is studied by quantum chemical calculations using the density functional theory. The topological analysis reveals that the electron density distributions are similar in both α- and β-trans-Pd(mki)2 complexes. Based on the analysis of intermolecular interactions it is shown that different molecular geometries of the α and β modifications of trans-Pd(mki)2 results in differences in structure-forming intermolecular contacts and consequently, affects the crystal molecular packing.

Проведен сравнительный кристаллохимический анализ летучих гомолигандных комплексов Co(II), Ni(II), Cu(II), Pd(II) и Pt(II) с β-кетоиминами, используемых в качестве предшественников для получения пленочных оксидных и металлических покрытий различного назначения методом газофазного осаждения (МОCVD). Изучены особенности кристаллического строения и межмолекулярные взаимодействия β-кетоиминатов с общей формулой М(L)2, где L = (R1-C(O) CH-C(N-R3)-R2)2, R1 и R2 = CH3, CF3, C(CH3)3, C(OCH3)(CH2)2 в различной комбинации, R3 = Н, CH3.

Heteroleptic copper(I) tetrafluoroborate complexes with pyrazolo[1,5-a][1,10]phenanthrolines (Ln, n = 1–3) and bis[(2-diphenylphosphino)phenyl] ether (POP) were synthesized and structurally characterized. The coordination compounds with the general formula [CuLn(POP)]BF4·Solv (n = 1, Solv = 0.5MeCN, complex I; n = 2, Solv = 0.5CH2Cl2, complex II; n = 3, Solv = 1.25Et2O, complex III·Et2O) were prepared by the reaction of CuBF4 with Ln and POP in organic solvents (MeCN/CH2Cl2/Et2O) at 1 : 1 : 1 molar ratio. Compound III·Et2O gradually loses solvate molecules to be converted to the complex [CuL3(POP)]BF4 (III). According to single-crystal X-ray diffraction data, the complexes (I, II, III·Et2O) are ionic; in complex cation [CuLn(POP)]+ the coordination environment of the copper atom is a distorted tetrahedron with CuN2P2 chromophore. The photoluminescence properties of the obtained complexes (I–III) were studied in the solid state and in solution. In the absorption spectra of the complexes, a charge transfer band is observed at 380–385 nm; excitation in this range gives rise to two emission bands at 480 and 650 nm in solution. In the solid state, the complexes show photoluminescence only in the red range (λmax = 600–610 nm) with microsecond lifetimes. It was found that complexes I and III with a more perfect tetrahedral environment have quantum yields an order of magnitude higher than the quantum yield observed for complex II.

New compounds (HOOC(CH2)5NH3)2SiF6 (1) and [Cu(Cpl)2(H2O)2SiF6]·2Cpl (2), where Cpl = ε-caprolactam ε-C6H11NO and (HOOC(CH2)5NH3)+ is the 5-carboxypentylammonium ion, were prepared from aqueous solutions and characterized by chemical analysis, IR spectroscopy, and single-crystal X-ray diffraction. In the structure of compound 1, the coordination surrounding of a Si atom is a nearly regular octahedron. The crystals of 1 are triclinic, space group P 1 . The caprolactam is hydrated and protonated upon crystallization. Hydrogen bonds F…Н–N between SiF_6^2 - anions and organic cations and acidic hydrogen bonds between the carboxy groups of cations were found to exist in the structure of 1. Compound 2 crystallizes in triclinic crystal system, space group P 1 , and has a chain-polymeric structure. The coordination polyhedra of the two unique copper ions are tetragonally distorted octahedra formed by the O atoms of two Cpl molecules and two F atoms of the hexafluorosilicate ions, which perform as bridges between nearest neighboring cations. The coordination surrounding around a Si atom is a slightly distorted octahedron. Hydrogen bonds between the H atoms of coordinated water molecules and the O atoms of uncoordinated Cpl molecules exist in the structure. The hexafluorosilicate ions in the structures of 1 and 2 have identical geometries.

We report a comparative crystal chemical analysis of volatile homoligand complexes of Co(II), Ni(II), Cu(II), Pd(II), and Pt(II) with β-ketoimines utilized as precursors in the preparation of oxide and metal film coatings for various purposes using chemical vapor deposition. The crystal structures and intermolecular interactions of β-ketoiminates with the general formula M(L)2 (L = (R1-C(O)CH-C(N-R3)-R2)2; R1, R2 = CH3, CF3, C(CH3)3, C(OCH3)(CH2)2 in various combinations; R3 = H, CH3) are studied.

Synthesis conditions were developed, new compounds of compositions (HOOC(CH2)5NH3)2SiF6 (1) and [Cu(Cpl)2(H2O)2SiF6]·2Cpl (2), where (Cpl – ɛ-caprolactam, ɛ-C6H11NO, (HOOC(CH2)5NH3)+ – cation 5-carboxypentylammonium) were obtained from aqueous solutions and studied by chemical, IR spectroscopic and X-ray diffraction analyses. In the structure of compound 1, the coordination environment of the Si atom is an almost regular octahedron. Crystals are triclinic sistem, space group P1¯. During crystallization, caprolactam undergoes a hydration reaction and protonation. In structure 1, hydrogen bonds F...H–N were found between anions and organic cations, as well as “acidic” hydrogen bonds between carboxyl groups of cations. Compound 2 crystallizes in the triclinic system, space group P1¯ and has a polymer chain structure. The coordination polyhedron of two independent copper cations is a tetragonally distorted octahedron formed by the O atoms of two Cpl molecules and two F atoms of hexafluorosilicate anions acting as bridges between neighboring cations. The coordination environment of the Si atom is a slightly distorted octahedron. The structure contains hydrogen bonds between the H atoms of coordinated water molecules and the O atoms of uncoordinated Cpl molecules. The geometry of hexafluorosilicate anions in structures 1 and 2 is identical.

Alkylation of tris(2,6-dimethoxyphenyl)stibine Ar3Sb, where Ar = 2,6-(MeO)2C6H3, with iodoethane in chloroform resulted in [Ar3EtSb]I, which further reacted with lead(II) nitrate to form [Ar3EtSb]NO3·0.75Н2О. The comparative characterization of the complexes was carried out by X-ray diffraction analysis, IR spectroscopy, and simultaneous thermal analysis. Antimony atoms in stibonium cations have a distorted tetrahedral coordination [CSbC angles 106.80(12)°–115.22(12)° and 105.33(14)°–115.33(14)°]. In a boiling aqueous solution, [Ar3EtSb]I and [Ar3EtSb]NO3·0.75Н2О decompose to tris(2,6-dimethoxyphenyl)stibine.

Кристаллографический анализ структур соединений Na2FePO4F (I), NaFePO4 (II) и LiVОPO4 (III) обнаружил вакантные каналы в «сотовых» конструкциях их катионных каркасов. В этих структурах основой стабильности служит последовательность вложенных друг в друга (по принципу «матрешки») псевдогексагональных конфигураций, связанных псевдосимметрией. Упорядочение позиций катионов создает их конфигурацию, приближающуюся к высокосимметричным подрешеткам, по геометрии близким к кубическим гранецентрированной (Fкуб.) и объемоцентрированной (Iкуб.). При этом в эквивалентных позициях оказываются разные атомы и вакансии.

A crystallographic analysis of two structures, monoclinic Nа 8 [{Re 4 (PO) 4 }(CN) 12 ]⋅18H 2 O⋅CH 3 OH ( I ) and orthorhombic [(C 6 H 5 ) 4 P] 4 [Ta 6 I 12 (CN 6 )] ( II ), in which clusters of heavy atoms are significantly rarefied in space, so that their mutual arrangement cannot be explained only in terms of chemical interaction, has been performed. In structure I the crystallographic planes with a high atomic density (“skeletal” planes) are located in the regions with d hkl = 10–5.5 Å and d hkl < 3 Å. The planes in which atomic groups [Re 4 (PO) 4 ] (playing the role of unified bulk objects) are concentrated are in fact selected in the first region. In the second region, ordering is implemented at the level of individual atoms. A crystallographic analysis showed that the structure basis is determined by the sites of heavy Re cations. A striking fact is that there are 1152 subcells and only 32 Re atoms per unit cell in this structure; i.e., only the fraction of 1/144 provides the basis of structure stability. In structure II “skeletal” planes are also absent in the range of d hkl from ∼7 to ∼4 Å. The planes in the range of large d hkl characterize cluster ordering, whereas the planes in the range of small d hkl characterize ordering of separate atoms. The geometry and local symmetry of the cluster group (Та 6 octahedron) dictates the basis of translational symmetry—unified sublattice of sites, most of which are free of these atoms. The considered structures demonstrate the key role of heavy atoms in the formation of translational symmetry—the fundamental difference of the crystalline state from other condensed states. The newly formed structure retains partially local symmetry of cores (templates) of atomic groups, bound by strong chemical interactions, including the interactions between heavy and light atoms. The process of formation of a crystal structure from randomly oriented and randomly located templates—coherence assembly—is implemented according to the laws of dynamics of elastic media, where masses of atoms rather than their chemical characteristics are important.

The crystallographic analysis of the structures of compounds Na 2 FePO 4 F ( I ), NaFePO 4 ( II ), and LiVOPO 4 ( III ) reveals that there are vacant channels in “honeycomb” constructions of their cation frameworks. In these structures, the stability is based on a sequence of embedded (according to the “matryoshka” principle) pseudosymmetry-related pseudo-hexagonal configurations. Ordering of cation positions creates their configuration approaching highly symmetrical sublattices that are close in geometry to face-centered ( F cube ) and body-centered ( I cube ) cubic sublattices. The equivalent positions are occupied by different atoms and vacancies.

The interpretation of translational symmetry as a consequence of the formation of a complex of standing planar elastic oscillations in atomic systems explains the stability of crystalline state. It supplements conventional crystallography with the energetic function of spatial symmetry, as well as reveals the mechanisms and sequence of atomic-site ordering. The standard technique of crystallographic analysis is demonstrated on the example of orthoborate structures: trigonal and monoclinic modifications of H3BO3 and hexagonal modification of Tl3BO3.

The complexes [AgL2]PF6 (I) and [ZnLCl2] (II) (L = 2-(3,5-dimethyl-1H-pyrazol-1-yl)-4,6-diphenylpyrimidine) were prepared by the reaction of zinc(II) chloride or silver(I) hexafluorophosphate with L (M : L molar ratio of 1 : 1 or 1 : 2) in organic solvents. The structure of the complexes was determined by X-ray diffraction (CIF file CCDC no. 2118498). In both complexes, L is coordinated in the bidentate chelating manner; the coordination unit is a distorted tetrahedron. The coordination unit of II is formed by one coordinated molecule L and two chloride ions (ZnN2Cl2); in the case of silver(I), there are two molecules L (AgN4). The photoluminescent properties of compounds I and II in the solid state were studied. The compound II shows fluorescence (1.3, 11 ns) in the blue spectral range (λmax = 378 nm; quantum yield of 7.8%). The maximum at 530 nm in the photoluminescence spectrum of I is red-shifted by ~140–160 nm relative to the emission maxima of L and II. The complex I shows white light emission (1.6, 11 ns, quantum yield of 5.5%), which is due to intraligand transitions perturbed by the coordination of L to the silver atom. The photostability of I was studied at 300 and 80 K.

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

As a result of the crystallographic analysis of the structures of borates BaNaSc(BO3)(2) (I) and K7CaY2(B5O10)(3) (II), a model of the formation of stable atomic groups (templates) with high point symmetry is proposed and a coherent assembly of these groups by the planes of pseudo cubic cation sublattices with the point symmetry spread on the whole structure is shown.

Методом рентгеноструктурного анализа впервые определена кристаллическая структура комплексной соли [Pt(NH3)4]3Mo7O24·5.5H2O. Изучен процесс термического разложения комплексного соединения в восстановительной и инертной атмосферах. Определены промежуточные и конечные продукты термодеструкции. Установлено, что при термолизе в восстановительной атмосфере формируется упорядоченный твердый раствор со структурой интерметаллида Mo2Pt3, а в инертной атмосфере конечный продукт представляет собой двухфазную смесь металлической платины и оксида молибдена(IV).

The crystal structure of the [Pt(NH3)4]3Mo7O24·5.5H2O complex salt is determined for the first time by XRD. Thermal decomposition of this complex in reducing and inert atmospheres is studied. Intermediate and final products of thermal decomposition are determined. It is established that thermolysis in a reducing atmosphere leads to the formation of an ordered solid solution with the intermetallic Mo2Pt3 structure, while the final product of thermolysis in an inert atmosphere is a two-phase mixture of metallic platinum and molybdenum(IV) oxide.

The crystallographic analysis of the structures of Yb3(BO3(OH)6)·2H2O (I), Ba8Ni4[BP3O11(OH)2]4 (II), and Pb4(O(OH)2)SiO4 (III) shows that they are based on sublattices of heavy Yb, Ba, Pb cations with similar parameters and a significant fraction of vacant nodes, which provides the formation of bulk voids. The key role of these cations also manifests itself in the fact that they occupy special positions with fixed coordinates and a high local symmetry. The crystallization process is a coherent assembly of chemically stable cation groups formed in the precrystallization phase of a substance.

The model of the occurrence of translational symmetry as a complex of standing plane elastic waves, forming three-dimensional lattices of their intersection nodes, is proposed based on the results of a crystallographic analysis of popular structure types. Criteria of crystal structure stability, characterizing the reduction of atomic degrees of freedom, are proposed taking into account the additional symmetric atomic ordering in the unit-cell volume. The characteristics of some highly symmetrical structures with cubic or hexagonal symmetry are compared. It is proposed to refer to the process of formation of stable states by creating symmetric spatial configurations, which is universal for material particles, as crystal dynamics.

The crystallographic analysis of the structure of a new compound with the metal-organic framework (MOF) [Li2Zn2(bpy)(ndc)3] (bpy = 4,4′-bipyridine, ndc2– = naphthalene-1,4-dicarboxylate) shows that its stability is provided by a body-centered quasi-cubic lattice of nodes, one sixth of which is occupied by ZnO3N tetrahedra. The local concentration of vacant nodes forms bulk channels and cavities in the structure.

Double complexes [Ln(DMSO)8][Cr(NCS)6], where Ln = Nd (1), Eu (2), Gd (3), Dy(4), Ho (5), Lu (6), Tb (7), or Yb (8), synthesized by the reaction between aqueous solutions of Ln(NO3)3 and K3[Cr(NCS)6] and dimethyl sulfoxide C2H6SO (DMSO) have been studied by IR spectroscopy and single-crystal X-ray diffraction. Single crystals of compounds for XRD were obtained by isothermal recrystallization of complex powders from DMSO solutions. Compounds 1–8 are isostructural, crystallize in the triclinic system, space group P $$\overline 1 $$ . The crystal structure is island with [Ln(DMSO)8]3+ cations and [Cr(NCS)6]3– anions. The asymmetric unit comprises two cations and two anions. The coordination environment of the Ln atom consists of eight O atoms of DMSO molecules located at the vertices of a distorted square antiprism. In isolated [Cr(NCS)6]3– anions, the chromium(III) coordination polyhedron is close to a regular octahedron and consists of N atoms of six NCS ions. The center packing of complex cations and anions is a distorted NaCl structure.