Hydrogen‐bonded supramolecule of N,N′‐bis(4‐pyridylmethyl)oxalamide and a zigzag chain structure of catena‐poly[[[dichloridocobalt(II)]‐μ‐N,N′‐bis(4‐pyridylmethyl)oxalamide‐κ2N4:N4′] hemihydrate]

N,N′‐Bis(4‐pyridylmethyl)oxalamide, C₁₄H₁₄N₄O₂, exists as a dimer which is extended into a two‐dimensional network with other dimers through pyridine–amide hydrogen bonds. The crystal structure of the title coordination polymer, {[CoCl₂(C₁₄H₁₄N₄O₂)]·0.5H₂O}_n, features a one‐dimensional zigzag chain, in which the cobalt ion sits at a twofold symmetry position and adopts a tetrahedral geometry, and the bridging ligand lies on an inversion center and connects to Co^II ions in a bis‐monodentate mode. Furthermore, two interwoven chains create a cavity of ca 8.6 × 8.6 Å, which produces a three‐dimensional channel. Water molecules are held in the channel by hydrogen bonds.     

Crystallographic report: (4,4′‐Bipyridine)bis[bis(N,N‐diethyldithiocarbamato)zinc(II)]

The structure of [Zn(S₂CNEt₂)₂]₂(4,4′‐bipy) shows two independent dimeric molecules, one located about a centre of inversion, the other lying on a two fold axis containing the zinc atoms. Bidentate coordination by the dithiocarbamate ligands and a distorted square pyramidal geometry are found for two of zinc atoms whereas for the third zinc atom, the geometry is intermediate between square pyramidal and trigonal bipyramidal, a result that underscores the flexibility of coordination in these systems. Copyright © 2003 John Wiley & Sons, Ltd.     

Di‐μ‐hydroxido‐bis{[bis(6‐methyl‐2‐pyridylmethyl)(2‐phenylethyl)amine‐κ3N′,N′′,N′′′]copper(II)} bis(perchlorate)

The title compund, [Cu₂(OH)₂(C₂₂H₂₅N₃)₂](ClO₄)₂, is a copper(II) dimer, with two [CuL]²⁺ units [L is bis(6‐methyl‐2‐pyridylmethyl)(2‐phenylethyl)amine] bridged by hydroxide groups to define the {[CuL](μ‐OH)₂[CuL]}²⁺ cation. Charge balance is provided by perchlorate counter‐anions. The cation has a crystallographic inversion centre halfway between the Cu^II ions, which are separated by 3.0161 (8) Å. The central core of the cation is an almost regular Cu₂O₂ parallelogram of sides 1.931 (2) and 1.935 (2) Å, with a Cu—O—Cu angle of 102.55 (11)°. The coordination geometry around each Cu^II centre can be best described as a square‐based pyramid, with three N atoms from L ligands and two hydroxide O atoms completing the coordination environment. Each cationic unit is hydrogen bonded to two perchlorate anions by means of hydroxide–perchlorate O—H...O interactions.     

N,N′,N′′,N′′′‐Tetraethylterephthalamidinium bis(tetrazolate)

The crystal structure of the title 2:1 salt of tetrazole and a substituted terephthal­amidine, C₁₆H₂₈N₄²⁺·2CHN₄^?, contains an infinite network of hydrogen bonds, with short N?N distances of 2.820 (2) and 2.8585 (19) Å between the tetrazolate anion and the amidinium cation. Involvement of the lateral N atoms of the tetrazole in the hydrogen bonding appears to be a typical binding pattern for the tetrazolate anion.     

(2‐Aminoethanethiolato‐N,S)bis(ethylenediamine‐N,N′)cobalt(III) dinitrate

In the title compound, [Co(C₂H₆NS)(C₂H₈N₂)₂](NO₃)₂, the Co^III atom has a slightly distorted octahedral geometry, coordinated by one 2‐amino­ethane­thiol­ate and two ethyl­enedi­amine ligands. The three five‐membered chelate rings adopt a gauche conformation with the unfavoured (lel)₂(ob) form, which is ascribed to hydrogen bonds between the amine groups in the complex cation and the nitrate counter‐anions [N?O 2.900 (3)–3.378 (3) Å].     

Hydrogen‐bonded one‐dimensional networks in 1:1 complexes of N,N′‐bis(2‐pyridyl)aryldiamines with anilic acid

The 1:1 complexes N,N′‐bis(2‐pyridyl)­benzene‐1,4‐di­amine–anilic acid (2,5‐di­hydroxy‐1,4‐benzo­quinone) (1/1), C₁₆H₁₄N₄·C₆H₄O₄, (I), and N,N′‐bis(2‐pyridyl)­bi­phenyl‐4,4′‐di­amine–anilic acid (1/1), C₂₂H₁₈N₄·C₆H₄O₄, (II), have been prepared and their solid‐state structures investigated. The component mol­ecules of these complexes are connected via conventional N—H?O and O—H?N hydrogen bonds, leading to the formation of an infinite one‐dimensional network generated by the cyclic motif R(9). The anilic acid molecules in both crystal structures lie around inversion centres and the observed bond lengths are typical for the neutral mol­ecule. Nevertheless, the pyridine C—N—C angles [120.9 (2) and 120.13 (17)° for complexes (I) and (II), respectively] point to a partial H‐atom transfer from anilic aicd to the bispyridyl­amine, and hence to H‐atom disorder in the OHN bridge. The bispyridyl­amine mol­ecules of (I) and (II) also lie around inversion centres and exhibit disorder of their central phenyl rings over two positions.     

Double anomeric effects and a hydrogen‐bonded supramolecular motif in N,N′‐bis(3‐nitrophenyl)methanediamine

In the title compound, C₁₃H₁₂N₄O₄, the molecule lies on a crystallographic twofold axis. Molecules are linked into complex sheets parallel to (100) via one N—H...O and two C—H...O hydrogen bonds. Within the molecule, the 3‐nitroanilino fragment is essentially planar, and the C—N—C—N—C fragment assumes a nearly perpendicular/perpendicular conformation, with C—N—C—N torsion angles of 81.18 (18)°, which is controlled by a pair of adjacent anomeric interactions. The findings constitute the first demonstration of two anomeric effects existing in one N—C—N unit.     

fac‐Tricarbonyl[bis(2‐pyridylmethyl) ether‐N,O,N′]molybdenum(0)

Reaction of bis(2‐pyridylmethyl) ether with [Mo(CO)₃­(Me­CN)₃] in MeCN gives the title compound, [Mo(C₁₂H₁₂‐N₂O)(CO)₃], (I), as a yellow crystalline product. Compound (I) has been characterized by ¹H NMR and IR spectroscopy, and single‐crystal X‐ray crystallography. In contrast with other examples of low‐valent early transition metal complexes of ethers, the ether linkage of (I) appears relatively inert. Nevertheless, the weak donor property of the ether ligand is evidenced by a trans effect manifested as a short Mo—CO bond length for the carbonyl ligand trans to the ether ligand.     

Hydrogen‐bonded chains in 2,2,2‐trichloro‐N,N′‐bis(4‐methoxyphenyl)ethane‐1,1‐diamine and a three‐dimensional hydrogen‐bonded framework in 2,2,2‐trichloro‐N,N′‐bis(4‐chlorophenyl)ethane‐1,1‐diamine

In 2,2,2‐trichloro‐N,N′‐bis(4‐methoxyphenyl)ethane‐1,1‐diamine, C₁₆H₁₇Cl₃N₂O₂, molecules are linked into helical chains by N—H...O hydrogen bonds. Molecules of 2,2,2‐trichloro‐N,N′‐bis(4‐chlorophenyl)ethane‐1,1‐diamine, C₁₄H₁₁Cl₅N₂, are connected into a three‐dimensional framework by two independent Cl...Cl interactions and one C—H...Cl hydrogen bond.     

{μ‐N,N′‐Bis[2‐(dimethylamino)ethyl]oxamidato(2–)‐κ6N,N′,O′:N′′,N′′′,O}bis[(2,2′‐bipyridine‐κ2N,N′)copper(II)] bis(perchlorate)

In the crystal structure of the title complex, [Cu₂(C₁₀H₂₀N₄O₂)(C₁₀H₈N₂)₂](ClO₄)₂, the deprotonated dmaeoxd²⁻ ligand {H₂dmaeoxd is N,N′‐bis[2‐(dimethylamino)ethyl]oxamide} occupies an inversion centre at the mid‐point of the central C—C bond and is thus in a trans conformation. The two Cu^II atoms are located in slightly distorted square‐based pyramidal environments. The binuclear units interact with each other viaπ–π interactions to form a one‐dimensional chain extending in the c direction.     

Hydrogen‐bonded network structures in dipyridinium,bis(2‐methylpyridinium), bis(3‐methylpyridinium) and bis(4‐methylpyridinium) dioxidobis(oxydiacetato)uranate(VI)

Four complexes containing the [UO₂(oda)₂]²⁻ anion (oda is oxydiacetate) are reported, namely dipyridinium dioxidobis(oxydiacetato)uranate(VI), (C₅H₆N)₂[U(C₄H₄O₅)₂O₂], (I), bis(2‐methylpyridinium) dioxidobis(oxydiacetato)uranate(VI), (C₈H₈N)₂[U(C₄H₄O₅)₂O₂], (II), bis(3‐methylpyridinium) dioxidobis(oxydiacetato)uranate(VI), (C₈H₈N)₂[U(C₄H₄O₅)₂O₂], (III), and bis(4‐methylpyridinium) dioxidobis(oxydiacetato)uranate(VI), (C₈H₈N)₂[U(C₄H₄O₅)₂O₂], (IV). The anions are achiral and are located on a mirror plane in (I) and on inversion centres in (II)–(IV). The four complexes are assembled into three‐dimensional structures via N—H...O and C—H...O interactions. Compounds (III) and (IV) are isomorphous; the [UO₂(oda)₂]²⁻ anions form a porous matrix which is nearly identical in the two structures, and the cations are located in channels formed in this matrix. Compounds (I) and (II) are very different from (III) and (IV): (I) forms a layered structure, while (II) forms ribbons.     

A novel framework of N—H...Br hydrogen bonds forming Br(4,4′‐bipyridinium)4 supramolecular synthons: bis(4,4′‐bipyridinium) tris[tetrabromidoferrate(III)] bromide

In the asymmetric unit of the title compound, (C₁₀H₁₀N₂)₂[FeBr₄]₃Br, the Fe atoms are in a distorted tetrahedral environment. The crystal structure contains a novel arrangement of Br(4,4′‐bipyridinium)₄ supramolecular synthons assembled via short N—H...Br hydrogen bonds (H...Br = 2.55, 2.40, 2.38 and 2.55 Å), where four cations surround one nonbonded bromide ion in a tetrahedral arrangement. These synthons are further connected by hydrogen bonds using the remaining terminal NH hydrogens in each cation and the Br⁻ ions to form an adamantoid‐like network and thus produce a three‐dimensional supramolecular architecture with the [FeBr₄]⁻ ions located in the cavities. The structure shows no significant intermolecular Br...Br, Br...aryl or aryl–aryl interactions.     

fac,trans‐[(2,2′‐Bipyridine‐N,N′)tricarbonylrhenium(I)]‐μ‐(4,4′‐bipyridine)‐N:N′‐{chlorobis[1,2‐phenylenebis(dimethylarsine)]ruthenium(II)} bis(hexafluorophosphate) diacetone solvate

The crystal structure of the heterobimetallic title compound, [ReRuCl(C₁₀H₁₆As₂)₂(C₁₀H₈N₂)₂(CO)₃](PF₆)₂·2C₃H₆O, is described. Both metal centres have pseudo‐octahedral coordination geometries, with a facial arrangement of the carbonyl ligands at Re^I and a trans disposition of the diarsine ligands at Ru^II. The dihedral angle between the pyridyl rings of the 4,4′‐bi­pyridine bridging ligand is 13.9 (6)°.     

The supramolecular architecture in 4,4′‐bipyridinium bis(hydrogen oxalate)

The asymmetric unit of the title compound, C₁₀H₁₀N₂²⁺·2C₂HO₄⁻, consists of one half of a 4,4′‐bipyridinium cation, which has inversion symmetry, and a hydrogen oxalate anion, in which an intramolecular hydrogen bond exists. The cations and anions are connected by O—H...O, N—H...O and C—H...O hydrogen bonds, forming a two‐dimensional network, whereas π–π stacking interactions involving the 4,4′‐bipyridinium cations lead to the formation of a three‐dimensional supramolecular structure. An unusual deca‐atomic ring is formed between two hydrogen oxalate anions, which are linked side‐to‐side via O—H...O hydrogen‐bonding interactions.     

Two cobalt(II) supramolecular isomers based on N,N′‐bis(pyridin‐3‐yl)oxalamide induced by the molecular orientation of lattice DMF molecules

Supramolecular isomerism for coordination networks refers to the existence of different architectures having the same building blocks and identical stoichiometries. For a given building block, different arrangements can lead to the formation of a series of supramolecular isomers. Two one‐dimensional Co^II coordination polymers based on N,N′‐bis(pyridin‐3‐yl)oxalamide (BPO), both catena‐poly[[[dichloridocobalt(II)]‐bis[μ‐N,N′‐bis(pyridin‐3‐yl)oxalamide‐κ²N:N′]] dimethylformamide disolvate], {[CoCl₂(C₁₂H₁₀N₄O₂)₂]·2C₃H₇NO}_n, have been assembled by the solvothermal method. Single‐crystal X‐ray diffraction analyses reveal that the two compounds are supramolecular isomers, the isomerism being induced by the orientation of the dimethylformamide (DMF) molecules in the crystal lattice.     

[N,N′‐Bis(3‐aminopropyl)ethylenediamine‐κ4N,N′,N′′,N′′′](trithiocyanurato‐κ2N,S)zinc(II) ethanol solvate

In the crystal structure of the title compound, [N,N′‐bis(3‐­amino­propyl)­ethyl­enedi­amine‐κ⁴N,N′,N′′,N′′′][1,3,5‐triazine‐2,4,6(1H,3H,5H)‐tri­thionato(2−)‐κ²N,S]­zinc(II) ethanol sol­vate, [Zn(C₈H₂₂N₄)₂(C₃HN₃S₃)]·C₂H₆O, the Zn^II atom is octa­hedrally coordinated by four N atoms [Zn—N = 2.104 (2)–2.203 (2) Å] of a tetradentate N‐donor N,N′‐bis(3‐­amino­propyl)­ethyl­enedi­amine (bapen) ligand and by two S and N atoms [Zn—S = 2.5700 (7) Å and Zn—N = 2.313 (2) Å] of a tri­thio­cyanurate(2−) (ttcH²⁻) dianion bonded as a bidentate ligand in a cis configuration. The crystal structure of the compound is stabilized by a network of hydrogen bonds.     

Hydrogen‐bonded network in biphenyl‐4,4′‐diphosphonic acid

The crystal structure of the title compound, C₁₂H₁₂O₆P₂, displays two different regions alternating along the a axis: a hydrogen‐bonded region encompassing the end‐positioned phosphonic acid groups and a hydrophobic region formed by the aromatic spacers. The asymmetric unit contains only half of the biphenyl‐4,4′‐diphosphonic acid (4,4′‐bpdp) molecule, which is symmetric with an inversion centre imposed at the mid‐point between the two aromatic rings. The periodic organization of the molecules is controlled by two strong O—H...O interactions between the phosphonic acid sites. Weak C—H...π interactions are established in the aromatic regions.     

Highly stable electrochromic polyamides based on N,N‐bis(4‐aminophenyl)‐N′,N′‐bis(4‐tert‐butylphenyl)‐1,4‐phenylenediamine

A new triphenylamine‐containing aromatic diamine monomer, N,N‐bis(4‐aminophenyl)‐N′,N′‐bis(4‐tert‐butylphenyl)‐1,4‐phenylenediamine, was synthesized by an established synthetic procedure from readily available reagents. A novel family of electroactive polyamides with di‐tert‐butyl‐substituted N,N,N′,N′‐tetraphenyl‐1,4‐phenylenediamine units were prepared via the phosphorylation polyamidation reactions of the newly synthesized diamine monomer with various aromatic or aliphatic dicarboxylic acids. All the polymers were amorphous with good solubility in many organic solvents, such as N‐methyl‐2‐pyrrolidinone (NMP) and N,N‐dimethylacetamide, and could be solution‐cast into tough and flexible polymer films. The polyamides derived from aromatic dicarboxylic acids had useful levels of thermal stability, with glass‐transition temperatures of 269–296 °C, 10% weight‐loss temperatures in excess of 544 °C, and char yields at 800 °C in nitrogen higher than 62%. The dilute solutions of these polyamides in NMP exhibited strong absorption bands centered at 316–342 nm and photoluminescence maxima around 362–465 nm in the violet‐blue region. The polyamides derived from aliphatic dicarboxylic acids were optically transparent in the visible region and fluoresced with a higher quantum yield compared with those derived from aromatic dicarboxylic acids. The hole‐transporting and electrochromic properties were examined by electrochemical and spectro‐electrochemical methods. Cyclic voltammograms of the polyamide films cast onto an indium‐tin oxide‐coated glass substrate exhibited two reversible oxidation redox couples at 0.57–0.60 V and 0.95–0.98 V versus Ag/AgCl in acetonitrile solution. The polyamide films revealed excellent elcterochemical and electrochromic stability, with a color change from a colorless or pale yellowish neutral form to green and blue oxidized forms at applied potentials ranging from 0.0 to 1.2 V. These anodically coloring polymeric materials showed interesting electrochromic properties, such as high coloration efficiency (CE = 216 cm²/C for the green coloring) and high contrast ratio of optical transmittance change (ΔT%) up to 64% at 424 nm and 59% at 983 nm for the green coloration, and 90% at 778 nm for the blue coloration. The electroactivity of the polymer remains intact even after cycling 500 times between its neutral and fully oxidized states. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 2330–2343, 2009     

Crystallographic report: Bis[bis(N,N‐dibenzyldithiocarbamato)zinc(II)](4,4′‐bipyridine)

The centrosymmetric structure of {Zn[S₂CN(CH₂Ph)₂]₂}₂(4,4′‐bipy) features chelating dithiocarbamate ligands so that a trigonal bipyramidal NS₄ coordination geometry for zinc results. Copyright © 2003 John Wiley & Sons, Ltd.     

μ‐4,4′‐Bipyridine‐κ2N:N′‐bis[triaqua(4,4′‐bipyridine‐κN)cadmium(II)] bis(3‐aminobenzoate) bis(perchlorate) dihydrate: a novel supramolecular system constructed by π–π and hydrogen‐bonding interactions

The title dicadmium compound, [Cd₂(C₁₀H₈N₂)₅(H₂O)₆](C₇H₆NO₂)₂(ClO₄)₂·2H₂O, is located around an inversion centre. Each Cd^II centre is coordinated by three N atoms from three different 4,4′‐bipyridine ligands and three O atoms from three coordinating water molecules in a distorted octahedral coordination environment. In the dicadmium cation unit, one 4,4′‐bipyridine (4,4′‐bipy) molecule acts as a bidentate bridging ligand between two Cd metal ions, while the other four 4,4′‐bipy molecules act only as monodentate terminal ligands, resulting in a rare `H‐type' [Cd₂(C₁₀H₈N₂)₅(H₂O)₆] host unit. These host units are connected to each other viaπ–π stacking interactions, giving rise to a three‐dimensional supramolecular grid network with large cavities. The 3‐aminobenzoate anions, perchlorate anions and water molecules are encapsulated in the cavities by numerous hydrogen‐bonding interactions. To the best of our knowledge, this is the first example of a coordination compound based on both 4,4′‐bipyridine ligands together with discrete 3‐aminobenzoate anions.