Molecular structures and crystal packings of 2-styrylquinoxaline derivatives

The crystal and molecular structures of 2-styrylquinoxaline derivatives with different substituents in the styryl fragment are determined. The degree of planarity of the molecules studied varies in a very wide range, from 1.7° to 33.5°. In the ethylene fragment, the double bond is essentially localized. The bicycle-pedal disordering of the ethylene fragment is found in the crystals of the methoxy and oxyacetyl derivatives of 2-styrylquinoxaline. None of the packings contains packing motifs favorable for the photocycloaddition (PCA) reaction with single crystal retention. The crystal packings of these compounds and that of 2-(4-methylstyryl)quinoxaline are characterized by a stacking motif of the head-to-head type, which eliminates the possibility of PCA taking place with single crystal retention but is suitable for this reaction in polycrystalline films. The crystal packing of 2-(3,4-dimethoxystyryl)quinoxaline does not contain elements with stacking interactions.     

Molecular structures and crystal packings of 2-styrylquinoline and its derivatives

The crystal and molecular structures of five styrylheterocycles of the quinoline series are studied. All molecules are planar. The double bond in the ethylene fragment is essentially localized. In the molecule of 2-(4-methylstyryl)quinoline, the ethylene fragment is disordered by the bicycle-pedal pattern. In four of the five compounds, the crystal packings do not contain stacking dimers prearranged for the [2+2] photocycloaddition (PCA) reaction. In the crystal of 2-(3-nitrostyryl)quinoline, pairs of crystallographically independent molecules form stacking dimers. In a dimer, the ethylene fragments have a twist orientation, which is incompatible with the PCA reaction. An attempt to initiate a temperature-dependent process of bicyclepedal isomerization in the crystal and, as a consequence, the PCA reaction by means of simultaneous irradiation and heating of a single crystal is unsuccessful.     

Supramolecular architecture of crown-containing styryl dyes: Part I. Crystal and molecular structures of the acetonitrile solvate monohydrate of the potassium iodide complex with benzo-15-crown-5 ether dye based on methylquinoline iodide

The structure of a single crystal of the acetonitrile solvate monohydrate of the potassium iodide complex with benzo-15-crown-5 ether dye based on methylquinoline iodide (I) is determined by X-ray diffraction. It is established that the single crystal contains positively charged molecules of benzocrown ether photodye (D), K⁺ cations, I^? anions, and water and acetonitrile solvate molecules in the ratio 1: 0.5: 1.5: 1: 1, respectively. The K⁺ cation and one of the I^? anions occupy special positions along the twofold axis. The K⁺ cation is coordinated by ten oxygen atoms of the crown ether fragments of two D molecules to form the [D ₂K]³⁺ complex. Inside the complex, two aromatic quinoline fragments are involved in a stacking interaction. The crossed mutual arrangement of the ethylene fragments and the considerable distance between them exclude the occurrence of intramolecular photochemical [2 + 2]cycloaddition reactions. In the crystal, the [D ₂K]³⁺ cationic complexes form stacks along the b axis. The adjacent complexes in a stack are related through the center of symmetry and, therefore, are arranged in a head-to-tail manner. The double bonds of the neighboring molecular cations D in a stack are strictly parallel to each other and are separated by a distance of 3.754 Å. This geometry is favorable to the intermolecular cycloaddition reaction that should result in the formation of the syn head-to-tail isomer.     

X-ray diffraction study of p-(alkoxybenzylidene)-p′-toluidines: Crystal and molecular structure of C10H21O-C6H4-CH=N-C6H4-CH3

The crystal and molecular structure of p-(decaoxybenzylidene)-p′-toluidine C₁₀H₂₁O-C₆H₄-CH=N-C₆H₄-CH₃ is studied. The molecule is nearly planar. In the crystal packing, loose regions formed by aliphatic fragments of molecules alternate with pseudostacks of aromatic fragments of molecules that are related by the centers of symmetry. The stacks are built of dimers, in which molecules are linked by π-stacking interactions between benzene rings. There are no weak directional interactions between dimers in a stack. The presence of a single structure-forming element in the crystal, namely, the π-stacking interactions in the dimers, along with the similarity of the crystal packing to that of the C₈H₁₇O-homologue, which forms a nematic mesophase on melting, indicate that the crystals under study should exhibit nematic properties.     

Molecular and crystal structure of 4-hexylbenzoic acid: Design of the mesophase

The crystal structure of 4-hexylbenzoic acid C₆H₁₃-C₆H₄-COOH, which forms a nematic mesophase upon melting, is determined. The crystal contains three crystallographically independent molecules. Their molecular skeletons are made up of two almost planar fragments: a benzene ring, π-conjugated with the carboxyl group and a planar zigzag aliphatic fragment. One of the independent molecules forms centrosymmetric dimers via pairs of hydrogen bonds between carboxyl groups, whereas the two others are linked via hydrogen bonds. The dimers in the crystal are packed into pseudostacks with a pronounced nonparallel arrangement of conjugated fragments. There is no good mutual projecting of benzene rings in the stacks, which corresponds to efficient π-stacking interaction. The graph describing the mesophase of this compound contains only one structure-forming element (a hydrogen bond) and corresponds to the nematic mesophase.     

Crystal and molecular structure of a series of 15-crown-5-containing styryl heterocycles and their dimethoxy substituted analogues

A comparative study of the molecular geometry and crystal packing of crown-containing styryl heterocycles and their dimethoxy substituted analogues is performed. It is established that all the compounds exhibit an identical type of distortions of the geometry of the central styryl fragment. These are the localization of the π-electron density at the ethylene bond and the bond alternation in a half of the phenyl ring due to the conjugation of lone electron pairs of the oxygen substituents with the chromophore system of the molecule. A comparative analysis of the crystal packings of the compounds reveals extended separate hydrophilic and hydrophobic regions. The hydrophilic regions are built of crown ether fragments, and the hydrophobic regions consist of π-conjugated and aromatic molecular fragments. The hydrophobic regions are characterized by a wide variety of packing motifs, among which stacking packing is absent. For two compounds, the formation of sandwich dimers that are preorganized to enter into the photochemical [2 + 2]cycloaddition reaction is observed.     

Synthesis,spectroscopic characterization and crystal structure of 5-bromo-1-(2-cyano-pyridin-4-yl)-1H-indazole-3-carboxylic acid diethylamide

The title compound 5-bromo-1-(2-cyano-pyridin-4-yl)-1H-indazole-3-carboxylic acid diethylamide, C₁₈H₁₆BrN₅O, is prepared from 5-bromoindazole-3-carboxylic acid methylester. N ¹-arylation is carried out with 4-chloro-2-cyanopyridine and the resulting product is converted to diethylamide by reacting with thionyl chloride and diethylamine. The structure is identified from its FT-IR, ¹H NMR, ¹³C NMR spectroscopy, elemental analysis data and unambiguously confirmed by single crystal X-ray diffraction studies. There are two symmetry independent molecules in the asymmetric unit with no significant differences in bond lengths and angles. The title compound crystallizes in the triclinic system, space group \(P\bar 1\) , with a = 11.2330(2); b = 11.6130(2); c = 15.4710(3) Å, α = 92.515(1)°; β = 109.956(1)°; γ = 107.199(1)°; V = 1788.45(6)ų and z = 4. An intramolecular C-H…N hydrogen bond forms an S(6) ring motif in one of the unique molecules. In the crystal, two molecules are linked about a center of inversion by C-H…O hydrogen bonded dimers generating an R ₂ ² (16) ring motif. The crystal packing is stabilized by C-H…N, C-H…O hydrogen bonds and π…π stacking interactions.     

Structural investigation of model compounds for an acceptor component of a new type of charge-transfer complexes based on viologen analogues. Characteristic features of the molecular and supramolecular structures

The crystal and molecular structures of six perchlorates (viologen analogues) are studied. These compounds serve as models of the acceptor component of new charge-transfer complexes containing bis(18-crown-6)stilbene as the donor. The polycyclic aromatic system of divalent cations is demonstrated to be virtually planar. In all cations, the side chains at the nitrogen atoms are oriented in opposite directions almost perpendicular to the plane of the cyclic system. This orientation of the spacers of these carbocations is indicative of their preorganization for the formation of 1: 2 charge-transfer complexes. Analysis of the crystal packings provides evidence that two positive charges on the conjugated systems of the organic cations and the perchlorate anions play a destructive role in the formation of stacking motifs. An increase in the size of the conjugated system and the involvement of an aromatic solvent molecule as an additional building block in a supramolecular system are favorable for the formation of a stacking supramolecular architecture.     

Br···HN, N···HC, Br···HC, and Br···Br intermolecular interactions as supramolecular synthons: Synthesis and crystal structure of bis(2-amino-5-methylpyridinium) tetrabromomercurate(II)

The bis(2-amino-5-methylpyridinium) tetrabromomercurate(II) (C₆H₉N₂)₂[HgBr₄] salt is triclinic, P1, with the following cell parameters: a=8.060(8) ?, b=9.035(9) ?, c=14.964(10) ?, α=96.032(19)°, β=90.317(15)°, γ=113.32(2)°, V=993.8(15) ?³, with Z=2 formula units. The crystal structure consists of alternating stacks of inorganic HgBr₄ ²⁻ anions and organic layers of 2-amino-5-methylpyridinium cations parallel to c-axis. The cohesion forces that connect molecules in the organic layers are N···HC hydrogen bonding and π–π stacking. The HgBr₄ ²⁻ units in the inorganic stacks are attracted via Br···Br intermolecular interactions.Supplementary material CCDC 270395 contains the supplementary crystallographic data. These data can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif, or by e-mailing at data_request@ccdc.cam.ac.uk, or by contacting the Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: + 44(0)1223-336033.     

Molecular and crystal structures of calix[4]arene 1,3-di-<Emphasis Type="Italic">n</Emphasis>-propyl ether

The molecular and crystal structures of calix[4]arene 1,3-di-n-propyl ether are determined. The molecule adopts a cone conformation stabilized by a pair of hydrogen bonds of the O-H?OR type (R is n-propyl). The dihedral angles between the planes of the benzene rings and the plane passing through the oxygen atoms are equal to 35.0°, 68.5°, 39.8°, and 71.2°. The larger angles are characteristic of the rings consisting of the ether groups, whereas the smaller angles are observed in the phenol rings. The bond lengths and angles in the molecule have standard values. In the crystal, the molecules form centrosymmetric dimers due to stacking interactions between two benzene rings in each dimer. Each of these rings is enclosed in the cavity of the other molecule in the dimer. The dimers have the shape of an ellipsoid. The packing as a whole can be described as an ellipsoid packing in which all the contacts occur through van der Waals interactions.     

Supramolecular architecture of two charge-transfer complexes based on 2,7-(X, X)-4,5-dinitro-9-dicyanomethylenefluorenes (X = NO2 or CN) and tetrathiafulvalene

The crystal packings of two charge-transfer complexes based on tetrathiafulvalene and substituted fluorenes-2,4,5,7-tetranitro-9-dicyanomethylenefluorene (in complex I) or 2,7-dicyano-4,5-dinitro-9-dicyanomethylenefluorene (in complex II)— are analyzed. Crystals of complex II involve a third component, namely, C₆H₅Cl solvate molecules. Crystals of both complexes are characterized by the formation of stacks composed of alternating donor and acceptor molecules and sheets in which the molecules are linked through different-type weak interactions. In structure II, chlorobenzene molecules occupy cavities that are formed in stacks in the vicinity of the tetrathiafulvalene molecules due to the larger difference in size of the donor and acceptor molecules in complex II as compared to that in complex I. The chlorobenzene molecules provide a close packing. These molecules are involved in the system of weak interactions to form the Cl?N and C-H?N secondary bonds with the CN groups of the acceptor molecules in the sheets.     

Molecular and crystal structure of mesomorphic para-n-hexyloxybenzoic acid

The triclinic modification of para-n-hexyloxybenzoic acid is studied using X-ray diffraction analysis (MoK _α radiation) at 120 K. The crystallographic parameters of the compound are as follows: space group, $P\overline 1 $ a = 7.8854(4) Å, b = 14.3021(7) Å, c = 33.0513(16) Å, α = 88.738(1)°, β = 85.701(1)°, γ = 78.331(1)°, and Z = 12. The asymmetric unit of the crystal contains six molecules of the acid with different orientations of the aliphatic chain. In the crystal, the molecules are joined into dimers by hydrogen bonds between the carboxyl groups. The crystal packing is built on the principle of the separation of aromatic and aliphatic regions.     

An X-ray investigation of growth and deformation faults in a vapour grown 2H SiC crystal

Single crystals of 2H SiC grown by hydrogen reduction of methyltrichlorosilane at 1400°C frequently contain a high concentration of random stacking faults in their hexagonal closepacked | AB | AB | … structure. This given rise to diffuse streaks along reciprocal lattice rows parallel to the c¹ axis for h ? k ≠ 0 mod 3. To investigate the nature of stacking faults in these crystals, the intensity distribution along the 10. l reciprocal lattice row of a 2H SiC crystal was recorded on a 4-circle computer-controlled single crystal diffractometer. The halfwidths of 10. l reflections with l even and l odd were found to be 0.36 and 0.24 reciprocal units respectively. It is observed (i) that the 10. l reflections with l even are highly broadened and (ii) that the halfwidths of l even and l odd reflections are in the ratio of 3 : 2. This suggests that the stacking faults present are predominantly growth and deformation faults. Since the fault concentration is very high, exact theoretical expressions for the halfwidths of 10. l reflections were used to calculate the growth and deformation fault probabilities (α and β) from the observed half widths, without neglecting the second and higher order terms in α and β. It is found that α = 0.11 and β = 0.20. The deformation fault probability (β) is surprisingly high for hard and brittle material like SiC which does not undergo plastic deformation easily. It is suggested that several deformation fault configurations have resulted from a clustering of growth faults.     

Relationship between the structure and luminescent properties for two crystal modifications of N-butyl-2-cyano-3-[4-(dimethylamino)phenyl]-2-propenamide

Two crystal modifications (1o and 1y) of N-butyl-2-cyano-3-[4-(dimethylamino)phenyl]-2-propenamide, which differ in the color of crystals and the color of luminescence, have been studied by X-ray diffraction and spectral-luminescence methods. The corresponding bond lengths and bond angles in the molecules of two crystal modifications are virtually identical. In both crystal structures, there are two systems of weak intermolecular interactions: π-stacking interactions and -CN…H-N hydrogen bonds involving nitrile and NH groups. In the crystal structures, two hydrogen bonds connect pairs of molecules into centrosymmetric dimers. The N…H distances are 2.21 and 2.41 Å in 1o and 1y, respectively. The interplanar distances in the π-stacked systems of 1o and 1y are 3.33 and 3.41 Å, respectively. Both types of weak interactions are stronger in 1o than in 1y, which accounts for a larger shift of absorption and luminescence bands for the former compound.     

Synthesis,growth conditions,and crystal structures of alkali metal hypophosphites <Emphasis Type="Italic">M</Emphasis>H<Subscript>2</Subscript>PO<Subscript>2</Subscript>

Metal hypophosphites are widely used in various fields. However, their structures have not been adequately studied. The synthesis conditions (the temperature and precursors) were found and crystals of anhydrous Li, K, Rb, Cs, and NH₄ hypophosphites were grown. The structures of these compounds were established by X-ray diffraction analysis. These crystal structures can be described as packings of layers consisting of hypo-phosphite anions coordinated to metal cations. In all these salts, the hypophosphite anions serve as bridges between four cations belonging to the same layer. Each oxygen atom is bound to two cations.     

Stereoselective Synthesis and X-Ray Structure Determination of Labeled [1, 2, 3-<Superscript>13</Superscript>C<Subscript>3</Subscript>]-1-(Phenylsulfinyl)-3-Benzyloxyacetone

[1,2,3-¹³C₃]-1-(Phenylsulfinyl)-3-benzyloxyacetone, C₁₆H₁₆O₃S, (3) has been synthesized and its crystal structure has been determined by a single-crystal X-ray diffraction analysis. The X-ray diffraction study revealed that compound 3 crystallizes in the monoclinic crystal system in the acentric space group Pc, with cell constants at T = 100 K: a = 16.073(5), b = 5.5079(16), c = 7.949(2) Å, β = 100.221(4)^°, V = 692.6(3) ų, Z = 2, d _calc = 1.383 g/cm³. Compound 3 contains the chiral tetravalent three-coordinated sulfur atom, which has a distorted tetrahedral configuration with a lone electron pair occupying one of the tetrahedron vertices. In the crystal, the molecules are packed in stacks along the b axis; the stacks consist of the molecules of the same chirality. Furthermore, the stacks of the molecules of the opposite chirality alternate along the c axis. The molecules in neighboring stacks are arranged by head-to-tail orientations. There are no short intermolecular contacts in the crystal of 3.     

Synthesis and crystal structure of 3,10-dimethyl-10H-dibenzo[b,e]iodinium tetrafluoroborate

The crystal and molecular structures of a chiral cyclic iodonium salt, namely, 3,10-dimethyl-10H-dibenzo[b,e]iodinium tetrafluoroborate, is solved by the direct method (a = 20.678(5) Å, b = 20.738(5) Å, c = 8.408(2) Å, γ =120.404(5)° Z = 4, sp. gr. P2₁/b). The crystals of the title compound consist of the iodonium cations and the BF ₄ ^? anions. The benzene rings A and B of the cations are planar. The angles between these rings are 56.1(4)° and 58.3(4)° in two independent molecules, and the rings are virtually coplanar with the corresponding halves of the central heterocycle C adopting the I,C(3)-boat conformation. The structural units are packed in the crystal so that each I atom forms short contacts with the fluorine atoms of two independent anions.     

(C2N2H10)2Mg(HP2O7)2·2H2O synthesis and crystal structure

(C₂N₂H₁₀)₂Mg(HP₂O₇)₂·2H₂O, is a new inorganic organic hybrid structure. It has been synthetized using wet chemistry. Its crystal structure consists of cis- and trans-edge sharing [MgO₄(H₂O)₂] octahedra resulting in chains, which are linked via [HP₂O₇] units to form [Mg(HP₂O₇)₂(H₂O)₂]⁴⁻ layers. The Mg²⁺ cations and the ethylendiammonium cations are located on centers of inversion. The ethylendiammonium cations are alternately located in the interlayer space. The cohesion of the crystal is well ensured by coulombic interactions between anions and cations and by several hydrogen bonds. The diphosphate anion shows an eclipsed conformation.     

Refinement of the crystal structure of lithium-bearing uvite

The crystal structure of a natural calcium tourmaline, i.e., uvite with a high lithium content (0.51 au per formula (aupf) at the Y site, is refined to R = 0.019, R _w = 0.020, and S = 1.11. It is shown that, in nature, there exist uvites in which the charge balance in the case where the Z site is occupied by trivalent cations is provided by the replacement of part of the divalent magnesium cations at the Y site by univalent cations, divalent calcium cations at the X site by sodium cations, and univalent anions at the W site by oxygen anions. The W site is found to be split into two sites, namely, the W1 and W11 sites (the W1–W11 distance is 0.14 Å), which are partially occupied by the fluorine and oxygen anions, respectively. An analysis of the results obtained in this study and the data available in the literature on the crystal structure of uvites allows the conclusion that uvite can be considered a superspecies and that the nomenclature of this mineral group needs refinement with the use of structural data.     

Conformational variability exhibited by mellitic acid anions (MA?n) with organic amine cations: Structures with an abundance of NH ?s OC hydrogen bonds and a paucity of hydrogen bonds

Benzenehexacarboxylic acid (mellitic acid) is an ideal substrate for the study of radially arranged ionic interactions with organic bases. Earlier work has shown that the net charge in MA (−4, −3, or −2) influences its assembly, respectively, either as ribbons or sheets. In the former case the cations intersperse the ribbons forming a tight network. In the MA sheets from the latter, the cations are arranged in orthogonal stacks. In the MA-phenanthroline complex such stacks are arranged exactly parallel resulting in significant π–π interactions. The present work relates to the modification of the phenanthroline motif to flexible structures. The reported ability of 2,3-bis-(2′-pyridyl) pyrazine (P2), prepared from 2,2′-pyridyl by reaction with ethylenediamine (EDA) followed by dehydrogenation of the resulting 2,3-bis-(2′-pyridyl)-5,6-dihydropyrazine, to form helical structures made it an obvious choice for complexation studies with MA. These resulted not only in the formation of the desired 7 MAP2 complex but also, surprisingly, with the dihydroprecursor complex with EDA 3 (MAEDA), a compound that eluded direct preparation with MA and EDA. The crystal structure of MAEDA reports the first complex of MA where MA⁻⁵ ions are encountered. The 15 hydrogen bonds, three for each N, result in hard packing. The complex with P2 7 (MAP2) showed the common features of MA⁻² sheets. Unlike phenanthroline, the nonplanar disposition of the pyridine rings made it possible for both pyridine protons to be available for salt formation, resulting in the arrangement of the cations in layers interposed between the sheets of MA⁻² ions. The pyrazine ring does not participate in hydrogen bonding or stacking in the crystal.