Two-dimensional Hydrogen-bonded Network Research Articles

Butane-1,4-diammonium dihydrogendecavanadate(V)

The crystal structure of (C4H14N2)2[H2V10O28] symmetry lying on a centre of symmetry, and two butane-1,4-diammonium cations per anion for charge compensation. The anion is protonated on centrosymmetrically related μ-OV3 groups; this is a less common protonation mode for dihydrogendeca­vanadates. Anions are involved in a two-dimensional hydrogen-bonding network, forming a layered structure.

Bis{4-[(4-pyridyl)ethenyl]pyridinium} 4-sulfonatobenzoate trihydrate

In the crystal structure of the title organic proton-transfer complex, 2C12H11N2 +·C7H4O5S2−·3H2O, the cations form one-dimensional chains via intermolecular N—H...N hydrogen bonds and these chains, in turn, form a two-dimensional network through π–π stacking interactions. In addition, the anions and water molecules are connected into a two-dimensional hydrogen-bonded network through intermolecular O—H...O hydrogen bonds. The two motifs result in sheets of cations and anions stacked alternately.

A two-dimensional strong hydrogen-bond network constructed from a transition metal with a polycarboxylato ligand

The supramolecular complex with mixed-ligands [Co2(1,2,4,5-btec)(2,2′-bipy)2(H2O)6] · 2H2O (1,2,4,5-btec = benzene-1,2,4,5-tetracarboxylic acid; 2,2′-bipy = 2,2′-bipyridine) was prepared and characterized by elemental analyses, IR spectra and X-ray single-crystal diffraction analysis. X-ray crystal structural analysis reveals that the compound belongs to the monoclinic system. C30H34Co2N4O16, P21/n, a = 12.2998(5) Å, b = 7.5943(3) Å, c = 17.9100(5) Å, α = 90.00°, β = 100.0790(3)°, γ = 90.00°, V = 1647.13(10) Å3, Z = 2. The complex is dinuclear with two Co atoms linked by two O atoms from one 1,2,4,5-benzenetetracarboxylate. In the unit of the structure, the two bipys are in same plane, and the dihedral angle with the benzene ring is 64.1°. There exist strong hydrogen bonds between the carboxylate oxygen atoms and coordinated water in the plane and weak H-bonding between the carboxylate oxygen atoms and H–C in the aromatic ring perpendicular to the plane.

(R)-1-Phenylethanaminium–(S,S)-2,3-dibromosuccinate–(R,R)-2,3-dibromosuccinic acid–water (2/1/1/2)

From an aqueous solution of racemic 2,3-dibromosuccinic acid and (R)-1-phenylethanamine, crystals of the title compound, C8H12N+·0.5C4H2Br2O4 2−·0.5C4H4Br2O4·H2O, were obtained in almost quantitative yield. The structure contains both enantiomers of the starting material, dibromosuccinic acid. The S,S enantiomer is present as a dianion and the R,R enantiomer as the neutral acid; both of these components lie on twofold rotation axes. The structure features a complex two-dimensional network of hydrogen bonds.

Orientational Control of Guest Molecules in an Organic Intercalation System by Host Polymer Tacticity

Four kinds of stereoregular poly(muconic acid)s, which are synthesized by topochemical polymerization and subsequent solid-state hydrolysis, are used as the organic host materials for intercalation. We describe the reaction behavior and layered structure of intercalation compounds using stereoregular poly(muconic acid)s and n-alkylamines as host and guest, respectively. The packing structure of the guest alkylamines was determined by X-ray diffractions as well as IR and Raman spectroscopies. We have found that the orientation of the guest molecules is controlled by the host polymer tacticity, depending on the structure of the two-dimensional hydrogen-bonding network formed in the polymer sheets of the crystals.

Designing a New Two‐Dimensional Molecular Layout by Hydrogen Bonding

Predetermined packing: The substitution of chlorine atoms for the surrounding hydrogen atoms of phthalocyanine determines the formation of molecular self-assembly at surfaces. The structure obtained after deposition (see image) is induced by the activation of an original two-dimensional hydrogen-bond network consisting of H⋅⋅⋅Cl bonds between neighboring molecules.

Tetrakis(benzylammonium) tetranitratocuprate(II) dinitrate

The crystal structure of the title compound, (C6H5CH2NH3)4[Cu(NO3)4](NO3)2, consists of alternating organic and inorganic layers. The aromatic groups constitute the organic layer, while the nitrate ions, ammonium groups and [Cu(NO3)4]2− anions form the inorganic layer; the complex anions lie on twofold rotation axes. Strong classical N—H⋯O hydrogen bonds in the inorganic layer result in a complex two-dimensional hydrogen-bonding network.

Structural characterization and magnetic properties of hexakis(imidazole)nickel(II) bis(formate), bis(chloroacetate), bis(2-chloropropionate) and hexakis(1-methyl-imidazole)nickel(II) chloride dihydrate

The nickel(II) complexes of formula [Ni(iz) 6]X 2, (where iz = imidazole, and X = formate, chloroacetate and 2-chloropropionate anions) have been prepared and characterized by spectroscopic methods and magnetic measurements. The crystal and molecular structure of [Ni(iz) 6](HCOO) 2, 1, [Ni(iz) 6](ClCH 2COO) 2, 2 and [Ni(iz) 6](CH 3ClCHCOO) 2, 3 have been determined by X-ray diffractions methods. The structure of the all complexes is formed by a three-dimensional network consisting of [Ni(iz) 6] 2+ cations interlinked by formate, chloroacetate and 2-chloropropionate anions through three different N–H⋯O bonds, in which all the N–H imidazole units, as well as all the carboxylate O atoms, take part. The Ni atom is in a nearly octahedral environment formed by the tertiary nitrogen atom of the imidazole moieties. An analogous complex [Ni(Meiz) 6]Cl 2 · 2H 2O ( 4) shows a two-dimensional hydrogen-bond network in which only four ligands take part along with Cl − and H 2O units. The distortion of Ni 2+ coordination polyhedron rises in the order of 1(negative) < 2 < 3(positive) < 4. The magnetism of complexes exhibits a zero-field splitting D, the magnitude of which correlates with the distortion degree of the coordination polyhedra.

Two-dimensional hydrogen-bonded networks in crystals of diboronic acids

Crystallization of suitable diboronic acids favors the formation of hydrogen-bonded sheets, thereby underscoring the usefulness of the –B(OH)2 group in crystal engineering.

Directing the Assembly of Molecular Crystals

AbstractCrystalline materials made from molecular components can possess useful properties that can be tailored through judicious selection of their molecular building blocks.The utility of these materials, however, depends on molecular packing in the crystal lattice as well as the properties of the individual molecules themselves. Consequently, further advances hinge on our ability to manipulate solid-state structure in a rational and systematic manner. Although computational prediction of crystal structure remains elusive, empirical guidelines for assembling molecules into preordained crystal architectures are emerging rapidly. This article briefly describes the current state of the field, emphasizing the design of crystalline materials with structures reinforced by a twodimensional hydrogen-bonded network, which serves as a platform for the synthesis of a diverse collection of compounds. These include host frameworks with cavities supported by organic “pillars” that can be interchanged to manipulate the size, shape, and character of the inclusion cavities as well as the overall lattice architecture and metrics. This research has revealed some principles for crystal design that may prove useful in general while enabling exploration of the utility of these compounds.

Crystal and Electronic Structures of Hydrogen-Bonded 2,5-Diamino-3,6-dihydroxy-p-benzoquinone

Shiny green-colored single crystals of 2,5-diamino-3,6-dihydroxy-p-benzoquinone (1) were prepared from 2,3,5,6-tetrahydroxy-p-phenylenediammonium dichloride. X-ray crystal structural analysis and ab initio calculations revealed that the molecular structure of 1, a highly polarized zwitterionic structure, was similar to that of p-benzoquinone rather than that of p-quinodiimine. Furthermore, a regular π-stack and an intermolecular two-dimensional hydrogen-bonding network were observed within the crystals of 1. The green color in the solid state was attributable to the intermolecular charge-transfer interactions.

Diacetatodiaquadioxouranium(VI) acetic acid disolvate

The coordination polyhedron of the U atom in the title compound, [U(C2H3O2)2O2(H2O)2]·2CH3COOH, is a distorted hexa­gonal bipyramid, with the equatorial positions occupied by four O atoms of two bidentate-chelating acetate anions and two O atoms of coordinated water mol­ecules. The complex lies on an inversion centre. A two-dimensional network of hydrogen bonds is present in the crystal structure.

(1,3-Diaminopropane-κ2N,N′)[tris(2-aminoethyl)amine-κ4N,N′,N′′,N′′′]nickel(II) bis(perchlorate)

In the title compound, [Ni(C3H10N2)(C6H18N4)](ClO4)2, the NiII atom has a distorted octa­hedral coordination, formed by four N atoms of the tris­(2-amino­ethyl)amine (tren) ligand and two N atoms of the 1,3-diamino­propane (pn) ligand. The tren ligand consists of three five-membered chelate rings in gauche conformations and the pn ligand consists of a six-membered chelate ring in a chair conformation. In the crystal structure, a two-dimensional network of hydrogen bonds extends parallel to the (100) plane.

2,9-Dichloro-5,12-dihydroquino[2,3-b]acridine-7,14-dione (red phase)

The title compound, C20H10Cl2N2O2, is one of the quinacridone derivatives known as a red pigment. The mol­ecule has inversion symmetry. The quinacridone molecules are connected by bifurcated N—H⋯O hydrogen bonds along [110] to form a two-dimensional hydrogen-bond network.

N-Propyl gallate–chloroform (3/0.5)

n-Propyl gallate (PG) is a charge-control agent used for toners in electrophotography, and shows pseudo-polymorphism. In the asymmetric unit of the title compound, 3 C10H12O5·0.5CHCl3, there are three PG mol­ecules and a half-mol­ecule of chloroform, the solvent molecule being disordered over an inversion centre. There are intra- and intermolecular O—H⋯O hydrogen bonds, forming a two-dimensional hydrogen-bond network in the (421) plane.

N-Propyl gallate–dichloromethane (3/0.5)

n-Propyl gallate (PG) is a charge-control agent used for toners in electrophotography, and shows pseudo-polymorphism. The title compound, 3C10H12O5·0.5CH2Cl2, is isostructural with the corresponding chloro­form solvate. The asymmetric unit is composed of three PG mol­ecules and a half-mol­ecule of dichloromethane, the solvent being disordered over an inversion centre. There are intra- and inter­molecular O—H⋯O hydrogen bonds, forming a two-dimensional hydrogen-bond network in the (421) plane.

Thiamine tetraphenylborate monohydrate: a two-dimensional hydrogen-bonded network with (4,4)-topology

The title compound, 3-[(4-amino-2-methylpyrimidin-5-yl)methyl]-5-(2-hydroxyethyl)-4-methylthiazolium tetraphenylborate monohydrate, C12H17N4OS+.C24H20B-.H2O, is a salt in which the thiamine cations are linked by hydrogen bonds into a two-dimensional network having (4,4)-topology. The stacked sheets form channels, which are occupied by the anions; the cations and anions are linked by C-H...pi(arene) hydrogen bonds.

Properties of Spanning Water Networks at Protein Surfaces

The formation of a spanning two-dimensional hydrogen-bonded water network at the surface of proteins via a percolation transition enables their biological function. We show in detail how the spanning (percolating) water network appears at the surfaces of model hydrophilic spheres and at the surface of a single protein (lysozyme) molecule. We have found essential correlations of the linear extension, radius of gyration, and position of the center of mass of the largest water cluster with its size. The specific two-peak structure of the probability distribution of the largest cluster size allowed us to study various properties separately for spanning and nonspanning largest clusters. The radius of gyration of the spanning cluster always exceeds the radii of the spheres or the effective radius of the protein. Any spanning cluster envelops essentially more than half of the surface area. The temporal decay of the spanning networks shows a stretched exponential character. Their average lifetime at the percolation threshold is about the lifetime of a water-water hydrogen bond.

Self-Assembly of Trimesic Acid at the Liquid−Solid Interfacea Study of Solvent-Induced Polymorphism

A scanning tunneling microscope operated under ambient conditions was utilized to study the self-assembly of trimesic acid (TMA) at the liquid-solid interface. On a graphite substrate, two different open, loosely packed, two-dimensional hydrogen-bond networks were found. Both structures exhibit a periodic arrangement of approximately 1.0 nm wide cavities, which can be used for the co-adsorption of another species (guest) within the cells of this host system. These two polymorphs ("chickenwire" and "flower" structures) differ in their molecular packing density and hydrogen-bonding schemes. Using a homologous series of alkanoic acids as solvents, ranging from butyric to nonanoic, selective self-assembly of either the "flower" or "chickenwire" forms was achieved on a graphite surface. Solubility of TMA in these acid solvents was found to decrease with increasing chain length, and the longer-chain solvents favored formation of the chickenwire polymorph structure on the surface.

Bis[tetraaqua(1,10-phenanthroline-κ2N,N′)cobalt(II)] 1,2,4,5-benzenetetracarboxylate

The title compound, [Co(C12H8N2)(H2O)4]2(C10H2O8), consists of discrete tetra­aqua­(1,10-phenanthroline)cobalt(II) cations and 1,2,4,5-benzene­tetra­carboxyl­ate anions. The CoII atom is octa­hedrally coordinated by two N atoms of the 1,10-phenanthroline ligand and four O atoms of water mol­ecules. The anion lies on an inversion centre. A two-dimensional hydrogen-bonding network is formed by O atoms of benzene­tetra­carboxyl­ate and the coordinated water mol­ecules.