Tetranaphthyleno[5,6‐bcd:11,12‐b′c′d′:17,18‐b′′c′′d′′:23,24‐b′′′c′′′d′′′]tetrafuran

The title compound, C₄₀H₁₆O₄ or [C₁₀H₄O]₄, is a planar tetrameric cyclooligomer which crystallizes in the monoclinic space group P2₁/n. The compound is located on an inversion center with the asymmetric unit consisting of half of the molecule. The compound displays an interesting packing structure, where the cyclooligomer displays both layered packing with respect to nearest neighbors and a rotation of adjacent planar rings that results in additional interactions. The geometric parameters of the compound agree well with those of comparable cyclooligomers, while the packing reveals some similarities and differences.     

4′‐Iodo‐2,2′:6′,2′′‐terpyridine

In the nearly planar title compound, C₁₅H₁₀IN₃, the three pyridine rings exhibit transoid conformations about the interannular C—C bonds. Very weak C—H...N and C—H...I interactions link the molecules into ribbons. Significant π–π stacking between molecules from different ribbons completes a three‐dimensional framework of intermolecular interactions. Four different packing motifs are observed among the known structures of simple 4′‐substituted terpyridines.     

4′‐Vinyl‐2,2′:6′,2′′‐ter­pyridine

The title compound, C₁₇H₁₃N₃, is a versatile precursor for polymeric ter­pyridine derivatives and their metal complexes. The mol­ecule has transoid and near‐coplanar pyridine rings. However, the vinyl group is forced out of the plane of the terpyridyl moiety by a close H?H contact.     

Synthesis and photophysical properties of 2,5,8,11‐tetrakis(5‐hexylthiophen‐2‐yl)tetrathieno[2,3‐a:3′,2′‐c:2′′,3′′‐f:3′′′,2′′′‐h]naphthalene

The title compound, C₅₈H₆₄S₈, has been prepared by Pd‐catalysed direct C—H arylation of tetrathienonaphthalene (TTN) with 5‐hexyl‐2‐iodothiophene and recrystallized by slow evaporation from dichloromethane. The crystal structure shows a completely planar geometry of the TTN core, crystallizing in the monoclinic space group P2₁/c. The structure consists of slipped π‐stacks and the interfacial distance between the mean planes of the TTN cores is 3.456 (5) Å, which is slightly larger than that of the comparable derivative of tetrathienoanthracene (TTA) with 2‐hexylthiophene groups. The packing in the two structures is greatly influenced by both the aromatic core of the structure and the alkyl side chains.     

Dispiro[indene‐2,5′‐indeno[2,1‐a]fluorene‐6′,2′′‐indene]‐1,1′′,3,3′′,11′,12′‐hexaone: a three‐dimensional hydrogen‐bonded framework

The title compound, C₃₆H₁₆O₆, (I), was obtained as a new and unexpected oxidation product of 1,2′‐biindene‐1′,3,3′(2H)‐trione. The molecules of (I) exhibit approximate, but noncrystallographic, twofold rotation symmetry and the central ring of the fused pentacyclic portion is distinctly puckered, with a conformation intermediate between half‐chair and screw‐boat. Six independent C—H...O hydrogen bonds link the molecules into a three‐dimensional framework structure of considerable complexity. Comparisons are drawn between the crystal structure of (I) and those of several simpler analogues, which show wide variation in their patterns of supramolecular aggregation.     

2,3,3′,6‐Tetra‐O‐acetyl‐4,1′,6′‐trichloro‐4,1′,4′,6′‐tetradeoxygalactosucrose

At 160 K, one of the Cl atoms in the furanoid moiety of 3‐O‐acetyl‐1,6‐di­chloro‐1,4,6‐tri­deoxy‐β‐d ‐fructo­furan­osyl 2,3,6‐tri‐O‐acetyl‐4‐chloro‐4‐deoxy‐α‐d ‐galacto­pyran­oside, C₂₀H₂₇­Cl₃O₁₁, is disordered over two orientations, which differ by a rotation of about 107° about the parent C—C bond. The conformation of the core of the mol­ecule is very similar to that of 3‐O‐acetyl‐1,4,6‐tri­chloro‐1,4,6‐tri­deoxy‐β‐d ‐tagato­furanos­yl 2,3,6‐tri‐O‐acetyl‐4‐chloro‐4‐deoxy‐α‐d ‐galacto­pyran­oside, particularly with regard to the conformation about the glycosidic linkage.     

2′‐Hydroxy‐4′′‐dimethylaminochalcone

The title compound, 3‐[4‐(di­methyl­amino)­phenyl]‐1‐(2‐hydroxy­phenyl)­prop‐2‐en‐1‐one, C₁₇H₁₇NO₂, is a chalcone derivative substituted by 2′‐hydroxyl and 4′′‐di­methyl­amino groups. The crystal structure indicates that the aniline and hydroxy­phenyl groups are nearly coplanar, with a dihedral angle of 10.32 (16)° between their phenyl rings. The molecular planarity of this substituted chalcone is strongly affected by the 2′‐hydroxyl group.     

(S,S)‐4′′‐Cyano‐7,7′′‐dimethoxy‐3′,6′‐dioxodispiro[indane‐2,2′‐piperazine‐5′,2′′‐indane]‐4‐carboxamide methanol solvate: interrupting the amide‐to‐amide hydrogen‐bonded tape

The title methanol solvate, C₂₄H₂₂N₄O₅·CH₃OH, forms an extended three‐dimensional hydrogen‐bonded structure, assisted by the presence of several good donor and acceptor sites. It shows none of the crystal packing features typically expected of piperazinediones, such as amide‐to‐amide R₂²(8) hydrogen bonding. In this structure the methanol solvent appears to play only a space‐filling role; it is not involved in any hydrogen bonding and instead is disordered over several sites. This study reports, to the best of our knowledge, the first crystal structure of an indane‐containing piperazinedione compound which exhibits a three‐dimensional hydrogen‐bonded structure formed by classical (N—H...O and N—H...N) hydrogen‐bonding interactions.     

4,4,4′,4′,7,7′‐Hexamethyl‐2,2′‐spirobichroman

The title compound, C₂₃H₂₈O₂, was obtained from the reaction of acetone with meta‐cresol. The molecular structure consists of two identical subunits which are nearly perpendicular to each other. The oxygen‐containing rings are not planar and the molecule is chiral. The crystal structure consists of chains of molecules of the same chirality arranged along the [010] axis.     

Flip‐type disorder in 3‐substituted 2,2′:5′,2′′‐terthiophenes

In the crystal structures of four thiophene derivatives, (E)‐3′‐[2‐(anthracen‐9‐yl)ethenyl]‐2,2′:5′,2′′‐terthiophene, C₂₈H₁₈S₃, (E)‐3′‐[2‐(1‐pyrenyl)ethenyl]‐2,2′:5′,2′′‐terthiophene, C₃₀H₁₈S₃, (E)‐3′‐[2‐(3,4‐dimethoxyphenyl)ethenyl]‐2,2′:5′,2′′‐terthiophene, C₂₂H₁₈O₂S₃, and (E,E)‐1,4‐bis[2‐(2,2′:5′,2′′‐terthiophen‐3′‐yl)ethenyl]‐2,5‐dimethoxybenzene, C₃₆H₂₆O₂S₆, at least one of the terminal thiophene rings is disordered and the disorder is of the flip type. The terthiophene fragments are far from being coplanar, contrary to terthiophene itself. The central C—C=C—C fragments are almost planar but the bond lengths suggest slight delocalization within this fragment. The crystal packing is determined by van der Waals interactions and some weak, relatively short, C—H...S and C—H...π directional contacts.     

Structural and theoretical characterization of a new twisted 4′‐substituted terpyridine compound: 4′‐(isoquinolin‐4‐yl)‐2,2′:6′,2′′‐terpyridine

4′‐Substituted derivatives of 2,2′:6′,2′′‐terpyridine with N‐containing heteroaromatic substituents, such as pyridyl groups, might be able to coordinate metal centres through the extra N‐donor atom, in addition to the chelating terpyridine N atoms. The incorporation of these peripheral N‐donor sites would also allow for the diversification of the types of noncovalent interactions present, such as hydrogen bonding and π–π stacking. The title compound, C₂₄H₁₆N₄, consists of a 2,2′:6′,2′′‐terpyridine nucleus (tpy), with a pendant isoquinoline group (isq) bound at the central pyridine (py) ring. The tpy nucleus deviates slightly from planarity, with interplanar angles between the lateral and central py rings in the range 2.24 (7)–7.90 (7)°, while the isq group is rotated significantly [by 46.57 (6)°] out of this planar scheme, associated with a short H_tpy…H_isq contact of 2.32 Å. There are no strong noncovalent interactions in the structure, the main ones being of the π–π and C—H…π types, giving rise to columnar arrays along [001], further linked by C—H…N hydrogen bonds into a three‐dimensional supramolecular structure. An Atoms In Molecules (AIM) analysis of the noncovalent interactions provided illuminating results, and while confirming the bonding character for all those interactions unquestionable from a geometrical point of view, it also provided answers for some cases where geometric parameters are not informative, in particular, the short H_tpy…H_isq contact of 2.32 Å to which AIM ascribed an attractive character.     

4,1′,6′‐Trichloro‐4,1′,6′‐trideoxysucrose monohydrate

At 160 K, the gluco­pyran­osyl ring in 1,6‐di­chloro‐1,6‐di­deoxy‐β‐d ‐fructo­furan­osyl 4‐chloro‐4‐deoxy‐α‐d ‐gluco­pyran­oside monohydrate, C₁₂H₁₉Cl₃O₈·H₂O, has a near ideal ⁴C₁ chair conformation, while the fructo­furan­osyl ring has a ⁴T₃ conformation. The conformation of the sugar mol­ecule is quite different to that of sucralose, particularly in the conformation about the glycosidic linkage, which affects the observed pattern of intramolecular hydrogen bonds. A complex series of intermolecular hydrogen bonds links the sugar and water mol­ecules into an infinite three‐dimensional framework.     

One‐dimensional CuII coordination polymers containing C2h‐symmetric 1,1′:4′,1′′‐terphenyl‐3,3′‐dicarboxylate linkers

Two new one‐dimensional Cu^II coordination polymers (CPs) containing the C_2h‐symmetric terphenyl‐based dicarboxylate linker 1,1′:4′,1′′‐terphenyl‐3,3′‐dicarboxylate (3,3′‐TPDC), namely catena‐poly[[bis(dimethylamine‐κN)copper(II)]‐μ‐1,1′:4′,1′′‐terphenyl‐3,3′‐dicarboxylato‐κ⁴O,O′:O′′:O′′′] monohydrate], {[Cu(C₂₀H₁₂O₄)(C₂H₇N)₂]·H₂O}_n, (I), and catena‐poly[[aquabis(dimethylamine‐κN)copper(II)]‐μ‐1,1′:4′,1′′‐terphenyl‐3,3′‐dicarboxylato‐κ²O³:O^3′] monohydrate], {[Cu(C₂₀H₁₂O₄)(C₂H₇N)₂(H₂O)]·H₂O}_n, (II), were both obtained from two different methods of preparation: one reaction was performed in the presence of 1,4‐diazabicyclo[2.2.2]octane (DABCO) as a potential pillar ligand and the other was carried out in the absence of the DABCO pillar. Both reactions afforded crystals of different colours, i.e. violet plates for (I) and blue needles for (II), both of which were analysed by X‐ray crystallography. The 3,3′‐TPDC bridging ligands coordinate the Cu^II ions in asymmetric chelating modes in (I) and in monodenate binding modes in (II), forming one‐dimensional chains in each case. Both coordination polymers contain two coordinated dimethylamine ligands in mutually trans positions, and there is an additional aqua ligand in (II). The solvent water molecules are involved in hydrogen bonds between the one‐dimensional coordination polymer chains, forming a two‐dimensional network in (I) and a three‐dimensional network in (II).     

Poly­[manganese(II)‐μ2‐benzidine‐κ2N:N′‐μ3‐bi­phenyl‐2,2′‐di­carboxylato‐κ4O:O′,O′′:O′′′]

The title compound, [Mn(C₁₄H₈O₄)(C₁₂H₁₂N₂)]_n, with a novel three‐dimensional framework, has been prepared by a hydro­thermal reaction at 433 K. Each Mn atom lies on a twofold axis in a slightly distorted octahedral geometry, coordinated by two N atoms from two benzidine ligands and four O atoms from three symmetry‐related biphenyl‐2,2′‐dicarboxylate (bpdc) ligands. The benzidine ligands lie about inversion centres and the bpdc ligands about twofold axes. Each bpdc ligand is bonded to three Mn ions to form a continuous chain of metal ions. The bpdc ligands are accommodated in a series of distorted holes resembling hexagonal prisms.     

Synthesis and Characterization of Fluorinated Polyimide Derived from 3,3′‐Diisopropyl‐4,4′‐diaminodiphenyl‐3′′,4′′‐difluorophenylmethane

A novel aromatic diamine monomer, 3,3′‐diisopropyl‐4,4′‐diaminodiphenyl‐3′′,4′′‐difluorophenylmethane (PAFM), was successfully synthesized by coupling of 2‐isopropylaniline and 3,4‐difluorobenzaldehyde. The aromatic diamine was adopted to synthesize a series of fluorinated polyimides by polycondensation with various dianhydrides: pyromellitic dianhydride (PMDA), 3,3′,4,4′‐biphenyltetracarboxylic dianhydride (BPDA), 4,4′‐oxydiphthalic anhydride (ODPA) and 3,3′,4,4′‐benzophenone tetracarboxylic dianhydride (BTDA) via the conventional one‐step method. These polyimides presented excellent solubility in common organic solvents, such as N,N‐dimethylformamide (DMF), N,N‐dimethyl acetamide (DMAc), dimethyl sulfoxide (DMSO), N‐methyl‐2‐pyrrolidone (NMP), chloroform (CHCl₃), tetrahydrofuran (THF) and so on. The glass transition temperatures (T_g) of fluorinated polyimides were in the range of 260–306°C and the temperature at 10% weight loss in the range of 474–502°C. Their films showed the cut‐off wavelengths of 330–361 nm and higher than 80% transparency in a wavelength range of 385–463 nm. Moreover, polymer films exhibited low dielectric properties in the range of 2.76–2.96 at 1 MHz, as well as prominent mechanical properties with tensile strengths of 66.7–97.4 MPa, a tensile modulus of 1.7–2.1 GPa and elongation at break of 7.2%–12.9%. The polymer films also showed outstanding hydrophobicity with the contact angle in the range of 91.2°–97.9°.     

1,1′‐Nitramino‐5,5′‐bitetrazoles

1,1′‐Dinitramino‐5,5′‐bitetrazole and 1,1′‐dinitramino‐5,5′‐azobitetrazole were synthesized for the first time. The neutral compounds are extremely sensitive and powerful explosives. Selected nitrogen‐rich salts were prepared to adjust sensitivity and performance values. The compounds were characterized by low‐temperature X‐ray diffraction, IR and Raman spectroscopy, multinuclear NMR spectroscopy, elemental analysis, and DTA/DSC. Calculated energetic performances using the EXPLO5 code based on calculated (CBS‐4M) heats of formation and X‐ray densities support the high performances of the 1,1′‐dinitramino‐5,5′‐bitetrazoles as energetic materials. The sensitivities toward impact, friction, and electrostatic discharge were also explored. Most of the compounds show sensitivities in the range of primary explosives and should only be handled with great care!     

3,3′‐Dinitro‐2,2′‐dithiodipyridine

In the title compound, C₁₀H₆N₄O₄S₂, (I), the molecule has a centre of inversion. The structure is a positional isomer of 5,5′‐dinitro‐2,2′‐dithiodipyridine [Brito, Mundaca, Cárdenas, López‐Rodríguez & Vargas (2007). Acta Cryst. E 63 , o3351–o3352], (II). The 3‐nitropyridine fragment of (I) shows excellent agreement with the bonding geometries of (II). The most obvious differences between them are in the S—S bond length [2.1167 (12) Å in (I) and 2.0719 (11) Å in (II)], and in the C—C_ipso—N_ring [119.8 (2)° in (I) and 123.9 (3)° in (II)] and S—C—C [122.62 (18)° in (I) and 116.0 (2)° in (II)] angles. The crystal structure of (I) has an intramolecular C—H...O interaction, with an H...O distance of 2.40 (3) Å, whereas this kind of interaction is not evident in (II). The molecules of (I) are linked into centrosymmetric R⁴₄(30) motifs by a C—H...O interaction. There are no aromatic π–π stacking and no C—H...π(arene) interactions. Compound (I) can be used as a nucleophilic tecton in self‐assembly reactions with metal centres of varying lability.     

Poly[triaqua(μ4‐4‐carboxybenzenesulfonato‐κ4O:O′:O′′:O′′′)(4‐carboxybenzenesulfonato‐κO)strontium(II)]

This study presents the coordination modes and two‐dimensional network of a novel strontium(II) coordination polymer, [Sr(C₇H₅O₅S)₂(H₂O)₃]_n. The eight‐coordinate Sr²⁺ ion is in a distorted bis‐disphenoidal coordination environment, surrounded by four sulfonate and one carboxyl O atom from five benzenesulfonate ligands, two of which are symmetry unique, and by three O atoms from three independent aqua ligands. The compound exhibits a monolayer structure with coordination bonds within and hydrogen bonds between the layers. The μ₄ acid ligand bridges the metal ions in two dimensions to form a thick undulating monolayer with a hydrophobic interior and hydrophilic surfaces. A second independent monoanion is arranged outward from both sides of the monolayer and serves to link adjacent monolayers via carboxyl–water and water–carboxyl hydrogen bonds.     

2,2′‐Dimeth­yl‐4,5′‐dinitro‐1H,3′H‐1,4′‐biimidazole monohydrate

The two almost perfectly planar imidazole rings in the title compound, C₈H₈N₆O₄·H₂O, make a dihedral angle of 63.01 (10)°. The water mol­ecule acts as a double donor and double acceptor of strong and linear hydrogen bonds, including an exceptionally short C—H⋯O bond. These bonds create a tight three‐dimensional structure and are probably responsible for the relatively high melting point of the compound.     

(3R*,3′R*)‐1,1′‐Dimethyl‐3,3′‐biindoline‐2,2′‐dithione

The (3R*,3′R*) configuration of the title compound, C₁₈H₁₆N₂S₂, (I), has been unambiguously elucidated by X‐­ray analysis. Mol­ecules of (I) have C₂ symmetry to a good approximation and a strongly folded shape. The interplanar angle between the two halves of a mol­ecule is 67.11 (6)°.