Peculiar reflections in diffraction patterns as indicators of structural type and quality

Reflections serving as indicators of the types of packets forming crystal structures of many layered semiconductors have been revealed in diffraction patterns. It is found that the values l for the strongest reflection in series 000l and 00l, as well as the next to the strongest reflection in series \(hh\bar 2\bar hl\) (h = const) and 0kl (k = const) for hexagonal and monoclinic structures, respectively, determine the number of polyhedral (Tand O) cation-filled layers per cell and indicate the types of packets TOT \(TO\bar TE\) , \(TO\bar T\bar TE\) , \(TOO\bar TE\) , \(TTO\bar T\bar TE\) , \(OOE_1 TO\bar TE_1 \) and OOE \(OOE_1 TO\bar TE_2 TO\bar TE_1 \) , where T and \(\bar T\) are inversely oriented tetrahedra, O is an octahedron, E is an empty interpacket layer, and E₁ and E₂ are partially filled (to less than 1/3) interpacket layers.     

New icosahedral nanoclusters in crystal structures of intermetallic compounds: Topological types of 50-atom deltahedra D50 in samson phases β-Mg2Al3 and ?-Mg23Al30

A database of intermetallic compounds has been compiled using the TOPOS program package. This database includes 514 topological types, containing 12- and 13-atom icosahedral i clusters. An isolated group of 1649 i clusters is described by 14 point groups and their maximum symmetry D _3d ( $\bar 3$ m) and T _h (m $\bar 3$ ) is established, respectively, in 47 and 25 types of crystal structures. A structural analysis of the outer quasispherical shells showed that local 63-atom i configurations 1@12@50, which contain 50 atoms in the second layer, are implemented in 8 out of 19 cases. Examples of new topologically different types of 50-atom D50 deltahedra in the Samson phases ?-Mg₂₃Al₃₀ and ??-Mg₂Al₃ are presented. Four topologically different sites with coordination numbers of 5, 6, 6, or 7 are established in the ? shell and seven sites with coordination numbers of 5, 5, 6, 6, 6, 6, or 7 are found in the ?? shell. The inner i clusters for the ??-Mg₂Al₃ structure (with the symmetry $\bar 3$ m) and the ?-Mg₂₃Al₃₀ structure (with the symmetry $\bar 3$ ) have a similar chemical composition, i.e., Mg₇Al₆ and Mg₆Al₇, and their 50-atom shells are chemically identical to 18Mg + 32Al. The configurations found supplement the series of known two-layer icosahedral Bergman and Mackay clusters in the form of deltahedra with 32- and 42-atom shells.     

Program for calculating the scattering parameters used in the X-ray standing wave method

A computer program for calculating the complex kinematic scattering parameters χ₀, χ_h, and $\chi _{\bar h} $ of X rays, which are Fourier components of the crystal complex susceptibility, as well as some of their combinations, is presented. The values calculated by the program can be used for computer simulation of experimental results obtained by the X-ray standing-wave method. Methods for calculating these parameters on the basis of well-known tables are described in detail. For crystals of complex structure, it is necessary to know their structure and the Debye temperature or specific heat capacity in order to calculate χ_h and $\chi _{\bar h} $ . To calculate χ₀, it is sufficient to know the chemical formula and the density of a material.     

The first observation of dislocation blocking in pure metal without external stress

Self-blocking of c + a edge dislocations at second-order pyramidal slip in magnesium single crystals whose axis is parallel to the c axis has been found. Self-blocking is confirmed by the dislocation extension along a selected direction in the absence of external stress. Transmission electron microscopy (TEM) images of (c + a) dislocations extended in the $\left\langle {1\bar 100} \right\rangle$ directions are obtained. A model of a two-valley potential relief in Mg is proposed: the Peierls relief determines the second-order slip of (c + a) dislocation in the pyramid plane, while the immersion in deep valleys is related to splitting of the c + a edge segment (or the spread of its core) in the basal plane.     

Structure analysis of O,O’-propane-1,3-diyl bis[diphenyl(phosphinothioate)]

A new diphosphine disulphide compound with the formula C₂₇H₂₆O₂|P₂S₂, was synthesized from the reaction between PPh₂SCl and 1,3-propanediol and characterized with different spectroscopic methods. Its structure has also been studied by X-ray diffraction. The compound crystallizes in the triclinic space group $P\bar 1$ . Pentavalent phosphorus atoms in the molecule are in distorted tetrahedral environments.     

2-Methylpyridinium/pyridinium 5-(2,4-dinitrophenyl)-2,6-dioxo-1,2,3,6-tetrahydropyrimidin-4-olates as potent anticonvulsant agents—synthesis and crystal structure

The molecular salt, 2-methylpyridinium 5-(2,4-dinitrophenyl)-2,6-dioxo-1,2,3,6-tetrahydropy-rimidin-4-olate) (I), is prepared from the ethanolic solution of 1-chloro-2,4-dinitrobenzene, pyrimidine-2,4,6-(1H,3H,5H)-trione (barbituric acid) and 2-methylpyridine at room temperature, and the molecular salt, pyridinium 5-(2,4-dinitrophenyl)-2,6-dioxo-1,2,3,6-tetrahydropyrimidin-4-olate (II), is prepared from the same reactants, by dissolving them in hot DMSO and ethanol mixture at 70°C. The structures of I and II are characterized by visible, IR, ¹H-NMR, ¹³C-NMR and elemental analysis and confirmed by single crystal X-ray analysis. Both the salts crystallize in triclinic crystal system with sp. gr. $P\bar 1$ . They possess noticeable anticonvulsant activity even at low concentration (25 mg/kg). Acute toxicity studies of these complexes indicate that LD₅₀ values are greater than 1500 mg/kg and the tested animals do not show any behavioural changes.     

Reaction of 2,3-bis(diphenylphosphino)maleic acid-thioanhydride (bmata) with PhCCo3(CO)9. X-ray diffraction structure of {\text{Co}}_{\text{3}} ({\text{CO)}}_{\text{6}} [\mu _2 ,\eta ^2 ,\eta ^1 {\text{ - C(Ph)}}{\text{(O)](}}\mu _2 {\text{ - PPh}}_{\text{2}} )

The benzylidyne-capped cluster PhCCo₃(CO)₉ (1) reacts with the diphosphine ligand 2,3-bis(diphenylphosphino)maleic acid-thioanhydride (bmata) to afford ultimately the new cluster ${\text{Co}}_{\text{3}} ({\text{CO)}}_{\text{6}} [\mu _2 ,\eta ^2 ,\eta ^1 {\text{ - C(Ph)}}{\text{(O)](}}\mu _2 {\text{ - PPh}}_{\text{2}} )$ (3) in low yield under thermolysis conditions or by Me₃NO activation of PhCCo₃(CO)₉. The intermediate cluster compound PhCCo₃(CO)₇(bmata) (2) has been confirmed by IR spectroscopy and is shown to give ${\text{Co}}_{\text{3}} ({\text{CO)}}_{\text{6}} [\mu _2 ,\eta ^2 ,\eta ^1 {\text{ - C(Ph)}}{\text{(O)](}}\mu _2 {\text{ - PPh}}_{\text{2}} )$ upon heating. Cluster 3 has been isolated and characterized in solution by IR and ³¹P NMR spectroscopies, and the solid-state structure of 3 was established by X-ray diffraction analysis. ${\text{Co}}_{\text{3}} ({\text{CO)}}_{\text{6}} [\mu _2 ,\eta ^2 ,\eta ^1 {\text{ - C(Ph)}}{\text{(O)](}}\mu _2 {\text{ - PPh}}_{\text{2}} )$ crystallizes in the triclinic space group P ${\bar 1}$ , a = 11.6053(8) Å, b = 11.8438(8) Å, c = 15.099(1) Å, α = 105.169(5)^○, β = 90.530(5)^○, γ = 104.976(6)^○, V = 1928.5(2) ų, Z = 2, and d _calc = 1.578; R = 0.0442, R _w = 0.481 for 2591 observed reflections with I > 3σ (I). The cyclic voltammetric properties of 3 have been investigated and are contrasted with the related bma-derived cluster ${\text{Co}}_{\text{3}} ({\text{CO)}}_{\text{6}} [\mu _2 ,\eta ^2 ,\eta ^1 {\text{ - }}{\text{(O)OC(O)](}}\mu _2 {\text{ - PPh}}_{\text{2}} )$ .     

Biscyclopentadienides with transition metal-mercury bonds. II: Dithiocarbamato derivatives of molybdenum and tungsten,and X-ray structure of (η5-C5H5)2Mo[HgS2CN(C2H5)2]2

The reactions in THF or benzene between Cp₂ M (HgX)₂ ·x HgX ₂ (M = Mo or W; O ?x ? 1;X ^? = Cl^?, Br^?, I^?, SCN^?, OAc^?) and sodium diethyl-dithiocarbamate $$\begin{gathered} Cp_2 M\left( {HgX} \right)_2 .xHgX_2 + \left( {2 + x} \right)Nadtc \rightleftharpoons Cp_2 M\left( {Hgdtc} \right)_2 \hfill \\ + xHg\left( {dtc} \right)_2 + \left( {2 + x} \right)NaX \hfill \\ \end{gathered} $$ as well as between Cp₂ MH₂ and mercury diethyldithiocarbamate $$x2Cp_2 MH_2 + 2Hg\left( {dtc} \right)_{2 - } Cp_2 M\left( {Hgdtc} \right)_2 + \left\{ {Cp_2 Mdtc} \right\}dtc + 2H_2 $$ give the compound Cp₂ M(Hgdtc)₂ (dtc is diethyldithiocarbamate anion). The structure of the molybdenum complex determined by the X-ray method (a = 12.776(4),b = 7.835(4),c = 27.397(7) Å β = 111.18(2) °; space groupC2/c (No. 15);Z = 4) consists of discrete molecules occupying special positions on two-fold axes. A short Mo-Hg distance of 2.643(8) Å and a rather long Hg-S one of 2.50(2) Å were found. The diethyldithiocarbamate anion behaves like a monodentate ligand. IR and¹H,¹³C NMR results agree with the molecular structure determination and confirm a weak bond between mercury and dithiocarbamate and strong molybdenum-mercury bond. A considerable solvent effect (C₆D₆ vs. CDCl₃ solutions) has been observed on the¹H chemical shifts of both dtc and Cp ligands. The {Cp₂Modtc}⁺ X ^? (X = dtc and PF₆) complexes, although not obtained in a pure form, were included in the discussion of the spectroscopic features of those with theM-Hg bonds.     

Phase transitions in bubble domain structures upon spin reorientation near the compensation point in ferrite-garnet films

The behavior of a hexagonal lattice of bubble domains in a uniaxial thin film of (BiTm)₃(FeGa)₅O₁₂ ferrite garnet with a compensation temperature of 120 K was studied experimentally in a range of change in anisotropy from the easy magnetization axis to the easy magnetization plane. It is shown that the spin reorientation occurs in the temperature range 185–160 K, in which the angular phase (either \(\Phi _{\left\langle {1\bar 1\bar 1} \right\rangle }\) or \(\Phi _{\left\langle {\bar 111} \right\rangle }\)) and the axial phase Φ:_〈111〉 coexist. At 172 K, when the percentages of the angular and axial phases are equal, the lattice parameters of the bubble domains and the domain-wall width change stepwise. At T < 160 K, only a plane magnetic phase exists.     

Refinement of the crystal structure of sanidine-like feldspar

The crystal structure of sanidine-like feldspar of the composition KAlSi₃O₈ from the Khibiny alkaline massif (the Kola Peninsula) has been refined (X-ray diffraction analysis; automated Syntex $P\bar 1$ diffractometer; 2θ: θ scanning technique; 2320 reflections; R _(hkl) = 0.0409; anisotropic refinement; AREN program package). The data obtained for KAlSi₃O₈ are: a = 8.615(9), b = 13.030(7), c = 7.200(5) Å, α = 89.99(5)°, β = 116.01(6)°, γ = 89.98(7)°, Z = 4, sp. gr. $C\bar 1$ . Microtwinning revealed in the crystal structure of the mineral explains the simultaneous existence of two structural-optical types in one sample—“high” and “low” sanidines.     

Crystal structure of 4-[benzylideneamino]-3-thiophen-2-yl-methyl-4,5-dihydro-1H-[1,2,4]triazole-5-one

The crystal structure of the title compound C₁₄H₁₂N₄OS was determined by the X-ray diffraction method. The compound crystallizes in the triclinic space group $P\bar 1$ with Z = 2. The molecule is not planar: the dihedral angle between the triazole and thiophene rings is 73.98(2)°, and that between the triazole and benzene rings is 4.05(2)°. The thiophene ring is disordered over two positions, which are approximately parallel and oppositely oriented. The major component refined to a site-occupancy factor of 0.573(3). An intramolecular C-H...O hydrogen bond generates an S(6) ring motif. In the crystal, molecules are linked together by two pairs of N-H...O interactions (to the same O atom as acceptor), forming inversion dimers. The crystal packing is also stabilized by π-π interactions [centroid-centroid distance is 3.978 Å].     

Flexoelectric effect and statistical properties in polar liquid crystals

The structural properties and flexoelectric coefficients e ₁ and e ₃ of polar liquid crystals (LCs) such as 4-n-pentyl-4′-cyanobiphenyl (5CB) are studied in the nematic phase by the molecular-dynamics and statistical-mechanics methods. A number of order parameters, $\bar P_{2L} (L = 1,2,3)$ and $\bar P_2 (r)$ , and orientational correlations ξ_λ for the nearest and next-nearest neighbors were investigated. The calculations show the absence of spontaneous polarization $(\bar P_1 \simeq 0)$ in the nondeformed polar 5CB liquid crystal over the entire range of temperatures corresponding to the nematic phase. The origination of spontaneous polarization (characterized by two independent flexoelectric coefficients e ₁ and e ₃) in response to an external deformation of a 5CB sample is studied. The calculated e ₁ and e ₃ coefficients agree well with the experimental data for 5CB obtained by the pyroelectric method.     

Formation of zinc oxide quasibicrystal structures

Quasibicrystal structures with interblock boundaries of epitaxial zinc oxide layers on a sapphire substrate along a given direction have been obtained for producing submicron electronic devices. It is shown that the use of the buffer technique allows one to grow on one (10 $\bar 1$ 2) α-Al₂O₃ substrate ZnO layers oriented in the (11 $\bar 2$ 0)and (0001) planes with clearly pronounced interlayer boundaries. The morphology and structural characteristics of these layers are studied.     

Structure of Tl18Pb2Ti7S25 as a masterpiece of crystallographic symmetry

A crystallographic analysis of the cubic structure of Tl₁₈Pb₂Ti₇S₂₅ has established the arrangement of all cations and anions according to the law of the 27-fold (with respect to volume) structure type of PbS(NaCl) with strictly fixed anionic vacancies. The nonintersecting axes of symmetry \(\bar 3\) of four directions organizing the structure distribute cations differing in sizes, charges, and amounts over general and particular sites of the sp. gr. Pa3 to form a high-symmetry design in the simple atomic matrix.     

Viscous and elastic properties of the nematic in the tetrapalladium organyl-pentadecane system

Temperature dependences of the dielectric anisotropy ?_a, effective rotational viscosity \(\tilde \gamma \), and elastic modulus K ₁₁ of the nematic phase of the tetrapalladium organyl-pentadecane system containing 55 wt % pentadecane have been experimentally studied. The quantities ?_a, \(\tilde \gamma \), and K ₁₁ are shown to decrease: ?_a decreases by a factor of about 2.5; \(\tilde \gamma \), by almost two orders of magnitude; and K ₁₁, by more than an order of magnitude. It is found that an applied electric field induces growth of tetrapalladium organyl crystals at 6–9°C above the nematic-crystallosolvate phase transition temperature.     

Alkylation of a bioinspired high spin Ni(II)N3S2 complex with bifunctional reagents

Crystal structures of two S-alkylated complexes generated from the reaction of iodoacetamide and iodoethanol with an air and moisture sensitive high spin Ni(II) pentacoordinate triaminodithiolate complex, 1 are determined by X-ray structure analysis. Crystals of complex 2, [NiC₁₆H₃₁N₅O₂S₂]I₂, are triclinic, sp. gr. $P\bar 1$ , Z = 2. Crystals of complex 3, [NiC₁₆H₂₈N₃O₂S₂]I₂, are monoclinic, sp. gr. P2₁/c, Z = 4. Structures of complexes 2 and 3 are very similar: one of the S-acetamide (2) or S-ethanol (3) groups coordinates to the Ni center through the oxygen atom forming N₃S₂O hexacoordination; the other group remains unbound to the Ni and left dangling. Crystal packing shows that complexes 2 and 3 interact with the iodide counterions, and that only complex 2 interact with neighboring molecules; some of these close intermolecular contacts include H-bonding interactions.     

Kinetics of hydrothermal crystallization of quartz in Na2CO3 solutions

The kinetics of crystallization of the {0001}c, {01 $\bar 1$ 1}r, and {10 $\bar 1$ 1}R faces of quartz in 0.5 M Na₂CO₃ (M is molarity) aqueous solutions has been studied in the temperature range 200–450°C. It is established that the dependence of the crystal growth rate on temperature in the logV-1/T, K coordinates is of a parabolic nature. It is most probable that the nonlinearity of this dependence is associated with a deficiency in the solution of silica monomers, taking part in the elementary event of quartz crystallization. The causes of a jumpwise decrease in the activation energy of the growth of the c, r, and R faces at t > 280–325°C are considered.     

Structure of tetrasodium nitrilotrimethylenetriphosphonatozincate tridecahydrate Na4[N(CH2PO3)3Zn] · 13H2O,an inhibitor of scaling and corrosion

The structure of a crystal hydrate of tetrasodium nitrilotrimethylenetriphosphonatozincate Na₄[N(CH₂PO₃)₃Zn] · 13H₂O is determined (space group $P\bar 1$ , Z = 2, a = 11.2208(2) Å, b = 11.2666(3) Å, c = 12.3286(3) Å, α = 108.455(2)°, β = 97.168(2)°, and = 117.103(2)°, Z = 2). The complex has a chelate structure; the inner coordination sphere includes three five-membered N-C-P-O-Zn cycles, which share the Zn-N bond. An oxygen atom of a neighboring complex completes a distorted trigonal bipyramidal coordination of the Zn atom.     

Synthesis, crystal structure and DFT studies of N-(4-acetyl-5,5-dimethyl-4,5-dihydro-1,3,4-thiadiazol-2-yl)acetamide

The title compound N-(4-acetyl-5,5-dimethyl-4,5-dihydro-1,3,4-thiadiazol-2-yl)acetamide (III) was obtained from the reaction of 2-(propan-2-ylidene)hydrazinecarbothioamide (II) with acetic anhydride instead of formation of the desired thiosemcarbazide derivative of Meldrum acid. The structures of II and III were established by elemental analysis, IR, NMR, Mass and X-ray crystallographic studies. II crystallizes in triclinic system, sp. gr. $P - \bar 1$ Z = 2; III crystallizes in the monoclinic system, sp. gr. P2₁/c, Z = 8. Density functional theory (DFT) calculations have been carried out for III. ¹H and ¹³C NMR of III has been calculated and correlated with experimental results.