Di- bis Pentahydrate von fünf Alkylendiaminen. Eine Fallstudie zu ein- und zweidimensionalen Wasserpolymeren in Festkörpern/Di- to Pentahydrates of Five Alkylenediamines. A Case Study of One- and Two-Dimensional Water Polymers in Solids

1999 ◽  
Vol 54 (1) ◽  
pp. 103-108 ◽  
Author(s):  
Stephanie Janeda ◽  
Dietrich Mootz
Keyword(s):  
Hydrogen Bonding ◽  
Hydrogen Bonds ◽  
Crystal Structures ◽  
Three Dimensional ◽  
Unit Cell ◽  
Water Molecules ◽  
Two Dimensional ◽  
Group I ◽  
Low Dimensional

The crystal structures of five low-melting hydrates of n-alkane-α,ω-diamines, H2N(CH2)nNH2 · x H2O, for short Cn · x W, have been determined. As a common feature, the water molecules are mutually linked by hydrogen bonds O-H· · ·O to form low-dimensional polymers. These are a meandering chain in C2 · 2 W (space group I 2/a, Z = 4 formula units per unit cell), a zig zag chain in C6 · 2 W (P 21/c, Z = 2), a ribbon of consecutively condensed five-membered rings in C3 · 3 W (P 21/c, Z = 4) and a layer of condensed and spiro-linked rings of varying size each in C7 · 3 W (P 1̄, Z = 4) and C4 · 5 W (C 2/c, Z = 4). Further hydrogen bonding, between the water polymers and the bifunctional amine molecules, leads to overall connectivities which are three-dimensional in each structure.

scholarly journals Crystal structures of tetramethylammonium (2,2′-bipyridine)tetracyanidoferrate(III) trihydrate and poly[[(2,2′-bipyridine-κ2N,N′)di-μ2-cyanido-dicyanido(μ-ethylenediamine)(ethylenediamine-κ2N,N′)cadmium(II)iron(II)] monohydrate]

2016 ◽  
Vol 72 (5) ◽  
pp. 741-746
Author(s):  
Songwuit Chanthee ◽  
Wikorn Punyain ◽  
Supawadee Namuangrak ◽  
Kittipong Chainok
Keyword(s):  
Hydrogen Bonds ◽  
Crystal Structures ◽  
Layer Structure ◽  
Three Dimensional ◽  
Building Blocks ◽  
Chain Structure ◽  
Water Molecules ◽  
Two Dimensional ◽  
Lattice Water ◽  
Π Stacking

The crystal structures of the building block tetramethylammonium (2,2′-bipyridine-κ2N,N′)tetracyanidoferrate(III) trihydrate, [N(CH3)4][Fe(CN)4(C10H8N2)]·3H2O, (I), and a new two-dimensional cyanide-bridged bimetallic coordination polymer, poly[[(2,2′-bipyridine-κ2N,N′)di-μ2-cyanido-dicyanido(μ-ethylenediamine-κ2N:N′)(ethylenediamine-κ2N,N′)cadmium(II)iron(II)] monohydrate], [CdFe(CN)4(C10H8N2)(C2H8N2)2]·H2O, (II), are reported. In the crystal of (I), pairs of [Fe(2,2′-bipy)(CN)4]−units (2,2′-bipy is 2,2′-bipyridine) are linked together through π–π stacking between the pyridyl rings of the 2,2′-bipy ligands to form a graphite-like structure parallel to theabplane. The three independent water molecules are hydrogen-bonded alternately with each other, forming a ladder chain structure withR44(8) andR66(12) graph-set ring motifs, while the disordered [N(CH3)4]+cations lie above and below the water chains, and the packing is stabilized by weak C—H...O hydrogen bonds. The water chains are further linked with adjacent sheets into a three-dimensional networkviaO—H...O hydrogen bonds involving the lattice water molecules and the N atoms of terminal cyanide groups of the [Fe(2,2′-bipy)(CN)4]−building blocks, forming anR44(12) ring motif. Compound (II) features a two-dimensional {[Fe(2,2′-bipy)(CN)4Cd(en)2]}nlayer structure (en is ethylenediamine) extending parallel to (010) and constructed from {[Fe(2,2′-bipy)(CN)4Cd(en)]}nchains interlinked by bridging en ligands at the Cd atoms. Classical O—H...N and N—H...O hydrogen bonds involving the lattice water molecule and N atoms of terminal cyanide groups and the N—H groups of the en ligands are observed within the layers. The layers are further connectedviaπ–π stacking interactions between adjacent pyridine rings of the 2,2′-bipy ligands, completing a three-dimensional supramolecular structure.

The isotypic hydrogen phosphate and arsenate dihydratesM2HXO4·2H2O (M= Rb, Cs;X= P, As)

2013 ◽  
Vol 70 (1) ◽  
pp. 7-11 ◽  
Author(s):  
Berthold Stöger ◽  
Matthias Weil
Keyword(s):  
Hydrogen Bonding ◽  
Hydrogen Bonds ◽  
Crystal Structures ◽  
Free Space ◽  
Three Dimensional ◽  
Water Molecules ◽  
Alkaline Metal ◽  
Hydrogen Phosphate ◽  
Dimensional Network ◽  
Medium Strength

The four isotypic alkaline metal monohydrogen arsenate(V) and phosphate(V) dihydratesM2HXO4·2H2O (M= Rb, Cs;X = P, As) [namely dicaesium monohydrogen arsenate(V) dihydrate, Cs2HAsO4·2H2O, dicaesium monohydrogen phosphate(V) dihydrate, Cs2HPO4·2H2O, dirubidium monohydrogen arsenate(V) dihydrate, Rb2HAsO4·2H2O, and dirubidium monohydrogen phosphate(V) dihydrate, Rb2HPO4·2H2O] were synthesized by reaction of an aqueous H3XO4solution with one equivalent of aqueousM2CO3. Their crystal structures are made up of undulating chains extending along [001] of tetrahedral [XO3(OH)]−anions connectedviastrong O—H...O hydrogen bonds. These chains are in turn connected into a three-dimensional networkviamedium-strength hydrogen bonding involving the water molecules. Two crystallographically differentM+cations are located in channels running along [001] or in the free space of the [XO3(OH)]−chains, respectively. They are coordinated by eight and twelve O atoms forming irregular polyhedra. The structures possess pseudosymmetry. Due to the ordering of the protons in the [XO3(OH)]−chains in the actual structures, the symmetry is reduced fromC2/ctoP21/c. Nevertheless, the deviation fromC2/csymmetry is minute.

Three-dimensional hydrogen-bonded assembly in 2,2′-disulfanylidene-5,5′-biimidazolidinylidene-4,4′-dione–dimethylformamide–water (3/2/4)

2013 ◽  
Vol 69 (12) ◽  
pp. 1545-1548 ◽  
Author(s):  
De-Hong Wu
Keyword(s):  
Hydrogen Bonding ◽  
Hydrogen Bonds ◽  
Three Dimensional ◽  
Dimensional Structure ◽  
Water Molecules ◽  
Two Dimensional ◽  
Hydrogen Bonding Interactions ◽  
Graph Set ◽  
Ribbon Structures ◽  
Hydrogen Bonded

The title compound, 3C6H4N4O2S2·2C3H7NO·4H2O, comprises three 2,2′-disulfanylidene-5,5′-biimidazolidinylidene-4,4′-dione molecules, two dimethylformamide molecules and four water molecules arranged around a crystallographic inversion centre. The non-H atoms within the 5,5′-biimidazolidinylidene molecule are coplanar and these molecules aggregate through N—H...S hydrogen-bonding interactions with cyclic motifs [graph setR22(8)], giving two-dimensional ribbon structures which are close to being parallel. The two independent water molecules associate to form centrosymmetric cyclic hydrogen-bonded (H2O)4tetrameric units [graph setR44(8)]. The ribbon structures extend along theaaxis and are linked through the water tetramers and the dimethylformamide molecules by a combination of two- and three-centre hydrogen bonds, giving an overall three-dimensional structure.

Thomsenolite, NaCaAlF6•H2O: hydrogen bonding and comparison with pachnolite

1985 ◽  
Vol 63 (12) ◽  
pp. 3322-3327 ◽  
Author(s):  
D. Adhikesavalu ◽  
T. Stanley Cameron ◽  
Osvald Knop
Keyword(s):  
Crystal Structure ◽  
Hydrogen Bonding ◽  
Hydrogen Bonds ◽  
Three Dimensional ◽  
Detailed Comparison ◽  
Water Molecules ◽  
Two Dimensional ◽  
Hydrogen Atoms ◽  
Hydrogen Bonding Network ◽  
Bonding Scheme

The crystal structure of thomsenolite, NaCaAlF6•H2O, has been redetermined to establish the hydrogen-bonding scheme in this mineral. Both hydrogen atoms participate in branched [Formula: see text] bonds. The hydrogen bonds link the AlF6, octahedra to form infinite chains ||b, which in turn are cross-linked to form infinite double sheets {[AlF6] + Ca}—(H2O)—{[AlF6] + Ca}||(001). The Na atoms are located exclusively in layers ||(001) which separate the double sheets. A detailed comparison of thomsenolite with its dimorph, pachnolite, shows that the structure of pachnolite is obtained in essence by interchanging the positions of one half of the Na atoms and one half of the water molecules in thomsenolite. The two-dimensional, layerlike hydrogen-bonding network in thomsenolite is thereby changed to one of a three-dimensional character in pachnolite. Other features of the two structures, including the Al—F and [Formula: see text] distances, are compared and discussed in some detail.

scholarly journals Crystal structures of {[Cu(Lpn)2][Fe(CN)5(NO)]·H2O}nand {[Cu(Lpn)2]3[Cr(CN)6]2·5H2O}n[where Lpn = (R)-propane-1,2-diamine]: two heterometallic chiral cyanide-bridged coordination polymers

2015 ◽  
Vol 71 (4) ◽  
pp. 392-397
Author(s):  
Olha Sereda ◽  
Helen Stoeckli-Evans
Keyword(s):  
Hydrogen Bonds ◽  
Coordination Polymers ◽  
Three Dimensional ◽  
Water Molecules ◽  
Two Dimensional ◽  
Asymmetric Unit ◽  
Compound I ◽  
Distorted Octahedral ◽  
Coordination Spheres ◽  
Compound Ii

The title compounds,catena-poly[[[bis[(R)-propane-1,2-diamine-κ2N,N′]copper(II)]-μ-cyanido-κ2N:C-[tris(cyanido-κC)(nitroso-κN)iron(III)]-μ-cyanido-κ2C:N] monohydrate], {[Cu(Lpn)2][Fe(CN)5(NO)]·H2O}n, (I), and poly[[hexa-μ-cyanido-κ12C:N-hexacyanido-κ6C-hexakis[(R)-propane-1,2-diamine-κ2N,N′]dichromium(III)tricopper(II)] pentahydrate], {[Cu(Lpn)2]3[Cr(CN)6]2·5H2O}n, (II) [where Lpn = (R)-propane-1,2-diamine, C3H10N2], are new chiral cyanide-bridged bimetallic coordination polymers. The asymmetric unit of compound (I) is composed of two independent cation–anion units of {[Cu(Lpn)2][Fe(CN)5)(NO)]} and two water molecules. The FeIIIatoms have distorted octahedral geometries, while the CuIIatoms can be considered to be pentacoordinate. In the crystal, however, the units align to form zigzag cyanide-bridged chains propagating along [101]. Hence, the CuIIatoms have distorted octahedral coordination spheres with extremely long semicoordination Cu—N(cyanido) bridging bonds. The chains are linked by O—H...N and N—H...N hydrogen bonds, forming two-dimensional networks parallel to (010), and the networks are linkedviaN—H...O and N—H...N hydrogen bonds, forming a three-dimensional framework. Compound (II) is a two-dimensional cyanide-bridged coordination polymer. The asymmetric unit is composed of two chiral {[Cu(Lpn)2][Cr(CN)6]}−anions bridged by a chiral [Cu(Lpn)2]2+cation and five water molecules of crystallization. Both the CrIIIatoms and the central CuIIatom have distorted octahedral geometries. The coordination spheres of the outer CuIIatoms of the asymmetric unit can be considered to be pentacoordinate. In the crystal, these units are bridged by long semicoordination Cu—N(cyanide) bridging bonds forming a two-dimensional network, hence these CuIIatoms now have distorted octahedral geometries. The networks, which lie parallel to (10-1), are linkedviaO—H...O, O—H...N, N—H...O and N—H...N hydrogen bonds involving all five non-coordinating water molecules, the cyanide N atoms and the NH2groups of the Lpn ligands, forming a three-dimensional framework.

scholarly journals Crystal structure and hydrogen bonding in the water-stabilized proton-transfer salt brucinium 4-aminophenylarsonate tetrahydrate

2016 ◽  
Vol 72 (5) ◽  
pp. 751-755 ◽  
Author(s):  
Graham Smith ◽  
Urs D. Wermuth
Keyword(s):  
Crystal Structure ◽  
Hydrogen Bond ◽  
Hydrogen Bonding ◽  
Hydrogen Bonds ◽  
Proton Transfer ◽  
Network Structure ◽  
Three Dimensional ◽  
Water Molecules ◽  
Arsanilic Acid ◽  
Dimensional Network

In the structure of the brucinium salt of 4-aminophenylarsonic acid (p-arsanilic acid), systematically 2,3-dimethoxy-10-oxostrychnidinium 4-aminophenylarsonate tetrahydrate, (C23H27N2O4)[As(C6H7N)O2(OH)]·4H2O, the brucinium cations form the characteristic undulating and overlapping head-to-tail layered brucine substructures packed along [010]. The arsanilate anions and the water molecules of solvation are accommodated between the layers and are linked to them through a primary cation N—H...O(anion) hydrogen bond, as well as through water O—H...O hydrogen bonds to brucinium and arsanilate ions as well as bridging water O-atom acceptors, giving an overall three-dimensional network structure.

Polymorphs of phenazine hexacyanoferrate(II) hydrate: supramolecular isomerism in a 2D hydrogen-bonded network

2021 ◽  
Vol 77 (2) ◽  
pp. 211-218
Author(s):  
Ivica Cvrtila ◽  
Vladimir Stilinović
Keyword(s):  
Hydrogen Bonding ◽  
Hydrogen Bonds ◽  
Crystal Structures ◽  
The Other ◽  
Two Dimensional ◽  
Structural Motifs ◽  
Supramolecular Isomerism ◽  
Other Hand ◽  
Π Stacking ◽  
Hydrogen Bonded

The crystal structures of two polymorphs of a phenazine hexacyanoferrate(II) salt/cocrystal, with the formula (Hphen)3[H2Fe(CN)6][H3Fe(CN)6]·2(phen)·2H2O, are reported. The polymorphs are comprised of (Hphen)2[H2Fe(CN)6] trimers and (Hphen)[(phen)2(H2O)2][H3Fe(CN)6] hexamers connected into two-dimensional (2D) hydrogen-bonded networks through strong hydrogen bonds between the [H2Fe(CN)6]2− and [H3Fe(CN)6]− anions. The layers are further connected by hydrogen bonds, as well as through π–π stacking of phenazine moieties. Aside from the identical 2D hydrogen-bonded networks, the two polymorphs share phenazine stacks comprising both protonated and neutral phenazine molecules. On the other hand, the polymorphs differ in the conformation, placement and orientation of the hydrogen-bonded trimers and hexamers within the hydrogen-bonded networks, which leads to different packing of the hydrogen-bonded layers, as well as to different hydrogen bonding between the layers. Thus, aside from an exceptional number of symmetry-independent units (nine in total), these two polymorphs show how robust structural motifs, such as charge-assisted hydrogen bonding or π-stacking, allow for different arrangements of the supramolecular units, resulting in polymorphism.

A 16-connected three-dimensional hydrogen-bonding network in tetrakis(4-aminopyridinium) perylene-3,4,9,10-tetracarboxylate octahydrate

2014 ◽  
Vol 70 (7) ◽  
pp. 668-671 ◽  
Author(s):  
Zhi-Hui Zhang ◽  
Jin-Long Wang ◽  
Ning Gao ◽  
Ming-Yang He
Keyword(s):  
Hydrogen Bonding ◽  
Hydrogen Bonds ◽  
Linear Chain ◽  
Three Dimensional ◽  
Organic Salt ◽  
Water Molecules ◽  
The Novel ◽  
One Dimensional ◽  
Connected Node ◽  
Hydrogen Bonding Network

The novel title organic salt, 4C5H7N2+·C24H8O84−·8H2O, was obtained from the reaction of perylene-3,4,9,10-tetracarboxylic acid (H4ptca) with 4-aminopyridine (4-ap). The asymmetric unit contains half a perylene-3,4,9,10-tetracarboxylate (ptca4−) anion with twofold symmetry, two 4-aminopyridinium (4-Hap+) cations and four water molecules. Strong N—H...O hydrogen bonds connect each ptca4−anion with four 4-Hap+cations to form a one-dimensional linear chain along the [010] direction, decorated by additional 4-Hap+cations attached by weak N—H...O hydrogen bonds to the ptca4−anions. Intermolecular O—H...O interactions of water molecules with ptca4−and 4-Hap+ions complete the three-dimensional hydrogen-bonding network. From the viewpoint of topology, each ptca4−anion acts as a 16-connected node by hydrogen bonding to six 4-Hap+cations and ten water molecules to yield a highly connected hydrogen-bonding framework. π–π interactions between 4-Hap+cations, and between 4-Hap+cations and ptca4−anions, further stabilize the three-dimensional hydrogen-bonding network.

Knowledge-based model of hydrogen-bonding propensity in organic crystals

2007 ◽  
Vol 63 (5) ◽  
pp. 768-782 ◽  
Author(s):  
Peter T. A. Galek ◽  
László Fábián ◽  
W. D. Samuel Motherwell ◽  
Frank H. Allen ◽  
Neil Feeder
Keyword(s):  
Hydrogen Bonding ◽  
Hydrogen Bonds ◽  
Crystal Structures ◽  
Three Dimensional ◽  
Chemical Properties ◽  
Organic Crystal ◽  
Training Data ◽  
Survey Method ◽  
Statistical Validation ◽  
Knowledge Based

A new method is presented to predict which donors and acceptors form hydrogen bonds in a crystal structure, based on the statistical analysis of hydrogen bonds in the Cambridge Structural Database (CSD). The method is named the logit hydrogen-bonding propensity (LHP) model. The approach has a potential application in identifying both likely and unusual hydrogen bonding, which can help to rationalize stable and metastable crystalline forms, of relevance to drug development in the pharmaceutical industry. Whilst polymorph prediction techniques are widely used, the LHP model is knowledge-based and is not restricted by the computational issues of polymorph prediction, and as such may form a valuable precursor to polymorph screening. Model construction applies logistic regression, using training data obtained with a new survey method based on the CSD system. The survey categorizes the hydrogen bonds and extracts model parameter values using descriptive structural and chemical properties from three-dimensional organic crystal structures. LHP predictions from a fitted model are made using two-dimensional observables alone. In the initial cases analysed, the model is highly accurate, achieving ∼ 90% correct classification of both observed hydrogen bonds and non-interacting donor–acceptor pairs. Extensive statistical validation shows the LHP model to be robust across a range of small-molecule organic crystal structures.

Hydrazonium(2+) hexafluorosilicate, N2H6SiF6: a NaCl-type structure with two-dimensional hydrogen-bonding networks

1983 ◽  
Vol 61 (1) ◽  
pp. 184-188 ◽  
Author(s):  
T. Stanley Cameron ◽  
Osvald Knop ◽  
Laura Ann MacDonald
Keyword(s):  
Hydrogen Bonding ◽  
Hydrogen Bonds ◽  
Bond Length ◽  
Room Temperature ◽  
Unit Cell ◽  
Type Structure ◽  
The Other ◽  
Effective Size ◽  
Two Dimensional ◽  
Hydrogen Bonding Networks

Hydrazonium(2+) hexafluorosilicate, N2H6SiF6, at room temperature has an orthorhombic (Pbca, Z = 4), pseudotetragonal unit cell (a = 7.605(1) Å, b = 7.586(2) Å, c = 8.543(1) Å). The structure consists of centrosymmetric N2H62+ and SiF62− ions arranged in a NaCl-type packing and connected by hydrogen bonds to two-dimensional N2H6–SiF6 layers parallel to (001). All H atoms are engaged in hydrogen bonding. Four of the six [Formula: see text] bonds to each cation are normal but significantly bent; the other two are trifurcated, [Formula: see text], but the out-of-layer component of the trifurcated bond is relatively unimportant. The N2H6SiF6 structure is compared in some detail with the structures of other hydrazonium(2+) salts, with particular attention to the N—N bond length, to the "effective" size of the N2H62+ ion, and to the tendency of this ion to form bent hydrogen bonds.

Sign in / Sign up

Export Citation Format

Share Document