Ksenia A. Paseshnichenko

Double stabilization of nanocrystalline silicon: a bonus from solvent

Double stabilization of the silicon nanocrystals was observed for the first time by 29Si and 13C MAS NMR spectroscopy. The role of solvent, 1,2-dimethoxyethane (glyme), in formation and stabilization of silicon nanocrystals as well as mechanism of modification of the surface of silicon nanocrystals by nitrogen-heterocyclic carbene (NHC) was studied in this research. It was shown that silicon nanocrystals were stabilized by the products of cleavage of the C–O bonds in ethers and similar compounds. The fact of stabilization of silicon nanoparticles with NHC ligands in glyme was experimentally detected. It was demonstrated that MAS NMR spectroscopy is rather informative for study of the surface of silicon nanoparticles but it needs very pure samples.Graphical Abstract

Tris(1-phenacyl-2-pyridone) Hydroxonium Tetrafluoroborate, a Hydrogen-Bonded Complex

The hydrolytic cleavage of 2-phenyloxazolo[3,2-a]pyridinium tetrafluoroborate results in the formation of the title tris(l-phenacyl-2-pyridone) hydroxonium tetrafluoroborate complex, 3C13H11NO2.H3O+.BF4-. The structure is built up from hydrogen-bonded cations and disordered BF4~ anions. The strong hydrogen bonding causes considerable redistribution of electron density in the pyridone moiety.

Zoledronic acid: monoclinic and triclinic polymorphs from powder diffraction data

The crystal structures of the monoclinic and triclinic polymorphs of zoledronic acid, C5H10N2O7P2, have been established from laboratory powder X-ray diffraction data. The molecules in both polymorphs are described as zwitterions, namely 1-(2-hydroxy-2-phosphonato-2-phosphonoethyl)-1H-imidazol-3-ium. Strong intermolecular hydrogen bonds (with donor-acceptor distances of 2.60 Å or less) link the molecules into layers, parallel to the (100) plane in the monoclinic polymorph and to the (1-10) plane in the triclinic polymorph. The phosphonic acid groups form the inner side of each layer, while the imidazolium groups lie to the outside of the layer, protruding in opposite directions. In both polymorphs, layers related by translation along [100] interact through weak hydrogen bonds (with donor-acceptor distances greater than 2.70 Å), forming three-dimensional layered structures. In the monoclinic polymorph, there are hydrogen-bonded centrosymmetric dimers linked by four strong O-H...O hydrogen bonds, which are not present in the triclinic polymorph.

Powder diffraction study of the hydrogen bonds in nitroxoline and its hydrochloride.

The crystal structures of 8-hydroxy-5-nitroquinoline, C9H6N2O3, (I), and 8-hydroxy-5-nitroquinolinium chloride, C9H7N2O3+*Cl-, (II), have been determined from X-ray powder data. In (I), the molecules are linked via moderately strong hydrogen bonds to form dimers. Such a packing motif is likely to be responsible for the low solubility of (I) in water. In (II), the inversion-related cations form stacks, and anions fill the interstack channels.

On the structure of luminol sodium salts

The structures of Tamerit® (A) and Galavit® (B) pharmaceutical preparations have been solved by X-Ray single crystal and powder diffraction. These are luminol sodium salts possessing immunomodulatory and anti-inflammatory properties. It is shown that Tamerit® (A) is a hydrated salt, while Galavit® (B) is a mixture of two polymorphic modifications (B1 and B2) of anhydrous salt. Compound A is crystallized in a monoclinic system: a = 8.3429(4) Å, b = 22.0562(11) Å, c = 5.2825(2) Å, β = 99.893(3)°, V = 957.59(8) Å3, and Z = 4; sp. gr. P21/c. Compound B1 is crystallized in a monoclinic system: a = 14.7157(18), b = 3.7029(19), c = 16.0233(15) Å, β = 116.682(13)°, V = 780.1(4) Å3, and Z = 4; sp. gr. P21/c. Compound B2 is crystallized in an orthorhombic system: a = 27.7765(15) Å, b = 3.3980(19) Å, c = 8.1692(19) Å, V = 771.0(5) Å3, and Z = 4; sp. gr. Pna21. The absence of phase transitions between the B1 and B2 polymorphs has been established by differential scanning calorimetry.

The twofold interpenetrated three-connected three-dimensional (10,3)-net in 2-aminoethene-1,1,2-tricarbonitrile.

In the crystal structure of the title compound, C5H2N4, each molecule is linked by N-H...N[triple-bond]C hydrogen bonds to four other molecules, thus forming a network that can be described as a twofold interpenetrated three-connected three-dimensional (10,3)-net. The interpenetrated nets are related by (010) translation. If only intermolecular hydrogen bonds are taken into account, these nets can be considered as independent. However, the interactions between the cyano groups from different nets indicate mutual assistance of the two nets during their formation.

Metabolic pathways of dithiocarbamates from laboratory powder diffraction data.

In order to correlate the reactivity and molecular structures of dithiocarbamates, the crystal structures of 6-dimethylamino-5-nitropyrimidin-4-yl N,N-diethyldithiocarbamate, C11H17N5O2S2, (Ia), and 6-methylamino-5-nitropyrimidin-4-yl N,N-diethyldithiocarbamate, C10H15N5O2S2, (Ib), and of the product of thermolysis of (Ib), namely 4-diethylamino-6-methylamino-5-nitropyrimidinium chloride monohydrate, C9H16N5(O2)(+).Cl(-).H2O, (II), have been determined from X-ray laboratory powder diffraction data. Conformational preferences in (Ia) and (Ib) were studied on the density functional theory (DFT) level. Deviation of the reaction centre of the molecule from planarity and breakage of the secondary S...O contact cause switching between two alternative pathways of thermolysis.

Sodium 4-(2-pyridinyldiazenyl)-resorcinolate monohydrate and ammonium 2,4-dinitro-1-naphthalenolate from powder diffraction data.

The crystal structures of two dyestuffs, Na(+).C(11)H(8)N(3)O(2)(-).H(2)O, (I), and NH(4)(+).C(10)H(5)N(2)O(5)(-), (II), were determined from X-ray powder diffraction data. In both structures, translationally related anions form stacks, and cations fill interstack channels. A comparison of the diffuse reflectance spectra of crystalline (I) and (II) with the absorption spectra of their aqueous solutions demonstrates that the geometry of their anions does not change significantly upon transfer from the crystalline to the solution state.

syn and anti conformations in 2-hydroxy-5-[(E)-(4-nitrophenyl)diazenyl]benzoic acid and two related salts.

The crystal structures of 2-hydroxy-5-[(E)-(4-nitrophenyl)diazenyl]benzoic acid, C13H9N3O5, (I), ammonium 2-hydroxy-5-[(E)-phenyldiazenyl]benzoate, NH4(+)·C13H9N2O3(-), (II), and sodium 2-hydroxy-5-[(E)-(4-nitrophenyl)diazenyl]benzoate trihydrate, Na(+)·C13H8N3O5(-)·3H2O, (III), have been determined using single-crystal X-ray diffraction. In (I) and (III), the phenyldiazenyl and carboxylic acid/carboxylate groups are in an anti orientation with respect to each other, which is in accord with the results of density functional theory (DFT) calculations, whereas in (II), the anion adopts a syn conformation. In (I), molecules form slanted stacks along the [100] direction. In (II), anions form bilayers parallel to (010), the inner part of the bilayers being formed by the benzene rings, with the -OH and -COO(-) substituents on the bilayer surface. The NH4(+) cations in (II) are located between the bilayers and are engaged in numerous N-H···O hydrogen bonds. In (III), anions form layers parallel to (001). Both Na(+) cations have a distorted octahedral environment, with four octahedra edge-shared by bridging water O atoms, forming [Na4(H2O)12](4+) units.

Two polymorphs of 2-ethyl-3-hydroxy-6-methylpyridinium hydrogen N-acetyl-L-glutamate from powder diffraction data.

The title salt, C8H12NO(+)·C7H10NO5(-), crystallizes in two polymorphic modifications, viz. monoclinic (M) and orthorhombic (O). The crystal structures of both polymorphic modifications have been established from laboratory powder diffraction data. The crystal packing motifs in the two polymorphs are different, but the conformations of the anions are generally similar. In M, the anions are linked by pairs of hydrogen bonds of the N-H···O and O-H···O types into chains along the b-axis direction, and neighbouring molecules within the chain are related by the 21 screw axis. The cations link these chains via O-H···O and N-H···O hydrogen bonds into layers parallel to (001). In O, the anions are linked by O-H···O hydrogen bonds into helices along [001], and neighbouring molecules within the helix are related by the 21 screw axis. The neighbouring helical turns are linked by N-H···O hydrogen bonds. The cations link the helices via O-H···O and N-H···O hydrogen bonds, thus forming a three-dimensional network.