Adducts of meso and racemic 5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane with trigonally trisubstituted benzene carboxylic acids: supramolecular structures in one and two dimensions

2000 ◽  
Vol 56 (6) ◽  
pp. 1054-1062 ◽  
Author(s):  
Colin J. Burchell ◽  
George Ferguson ◽  
Alan J. Lough ◽  
Christopher Glidewell
Keyword(s):  
Hydrogen Bonds ◽  
Carboxylic Acids ◽  
Supramolecular Structure ◽  
Two Dimensions ◽  
Supramolecular Structures ◽  
Acid Water ◽  
Water Molecules ◽  
One Dimensional ◽  
Space Groups

The meso and racemic forms of 5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane, C16H36N4 (tet-a and tet-b, respectively), form adducts with trigonally trisubstituted benzene carboxylic acids; tet-a–3,5-dinitrobenzoic acid (1/2) (1), tet-a–5-hydroxyisophthalic acid–water (1/1/1) (3) and tet-b–5-hydroxyisophthalic acid–water (1/1/1) (4) are all salts, [C16H38N4]2+·2[C7H3N2O6]− (1) and [C16H38N4]2+·[C8H4O5]2−·H2O (3) and (4). The conformations of the [(tet-a)H2]2+ and [(tet-b)H2]2+ cations are entirely different: [(tet-a)H2]2+ is precisely centrosymmetric in (1) and approximately so in (3), while [(tet-b)H2]2+ has approximate C 2 symmetry in (4). In each salt the cation forms two intramolecular N—H...N and four intermolecular N—H...O hydrogen bonds. In (1) the supramolecular structure is one-dimensional, a C 2 2(13)[R 2 4(16)] chain of rings. Compounds (3) and (4) crystallize in space groups P212121 and P21/c, respectively, but the supramolecular structures are very similar: in each, the anions and the water molecules form a C(7)[R 3 3(13)] chain of rings, generated in (3) by a 21 axis and in (4) by a glide plane. These chains are linked, in both (3) and (4), by cations to form sheets. Adjacent meso cations in (3) are related by a 21 axis and adjacent chiral cations in (4) are related by a glide plane.

Supramolecular structures in three thiouracil derivatives: 5,6-trimethylene-2-sulfanylidene-1,2-dihydropyrimidin-4(3H)-one, 2-(4-fluorobenzylsulfanyl)-5,6-trimethylenepyrimidin-4(3H)-one and methyl 2-{[2-(4-fluorobenzylsulfanyl)-5,6-trimethylenepyrimidin-4-yl]oxy}acetate

2014 ◽  
Vol 70 (4) ◽  
pp. 416-420 ◽  
Author(s):  
Yu-Jun Zhou ◽  
Jing Lv ◽  
Kai Yu ◽  
Jian-Ping Ma ◽  
Dian-Shun Guo
Keyword(s):  
Hydrogen Bonds ◽  
Supramolecular Structure ◽  
Three Dimensional ◽  
Supramolecular Structures ◽  
Asymmetric Unit ◽  
One Dimensional ◽  
Space Groups ◽  
Different Types ◽  
Independent Molecules ◽  
Thiouracil Derivatives

The molecules of the title compounds, C7H8N2OS, (1), C14H13FN2OS, (2), and C17H17FN2O3S, (3), crystallize in the space groupsC2/m,C2/candIa, respectively. Compounds (1) and (2), anS-alkylated derivative of (1), consist of only one symmetry-independent molecule, while (3), anO-alkylated derivative of (2), contains two independent molecules in the asymmetric unit. The molecules of (1) sit on crystallographic mirror planes. In the supramolecular structure of (1), a combination of N—H...O and N—H...S hydrogen bonds creates a molecular strap withC(6) andR22(8) motifs, which is further stabilized by an S...S contact. In the packing of (2), a one-dimensional molecular column is made up of two kinds of dimers. One dimer, with anR22(18) motif, is formed by a pair of C—H...O soft hydrogen bonds and the other, with anR22(8) motif, is producedviaa pair of N—H...O hard hydrogen bonds. In the packing of (3), moleculesAandBform two different types of one-dimensional chain by intermolecular C—H...N hydrogen bonds, and by C...N and O...S contacts, respectively. Two such kinds of chain are connected alternatelyviainterchain C—H...O hydrogen bonds, giving a two-dimensional sheet. Finally, a three-dimensional supramolecular structure is formed through weak intersheet C—H...F hydrogen bonds. The study of the molecular and supramolecular structures of thiouracil derivatives is significant in the development of lipoprotein-associated phospholipase A2inhibitors.

scholarly journals Diaqua(5,10,15,20-tetraphenylporphyrinato-κ4N)magnesium–18-crown-6 (1/1)

2013 ◽  
Vol 69 (2) ◽  
pp. m114-m115 ◽  
Author(s):  
Khaireddine Ezzayani ◽  
Soumaya Nasri ◽  
Mohamed Salah Belkhiria ◽  
Jean-Claude Daran ◽  
Habib Nasri
Keyword(s):  
Hydrogen Bonds ◽  
Bond Length ◽  
Title Compound ◽  
Supramolecular Structure ◽  
Crystal Packing ◽  
Water Molecules ◽  
Supramolecular Architecture ◽  
Inversion Center ◽  
Asymmetric Unit ◽  
One Dimensional

In the title compound, [Mg(C44H28N4)(H2O)2]·C12H24O6, the MgIIcation lies on an inversion center and is octahedrally coordinated by the four N atoms of the deprotonated tetraphenylporphyrin (TPP) ligand and by two water molecules. The asymmetric unit contains one half of the [Mg(TPP)(H2O)2] complex and one half of an 18-crown-6 molecule. The average equatorial magnesium–pyrrole N atom distance (Mg—Np) is 2.071 (1) Å and the axial Mg—O(H2O) bond length is 2.213 (1) Å. The crystal packing is stabilized by two O—H...O hydrogen bonds between coordinating water molecules and adjacent 18-crown-6 molecules, and exhibits a one-dimensional supramolecular structure along theaaxis. The supramolecular architecture is futher stabilized by weak C—H...π interactions. The 18-crown-6 molecule is disordered over two sets of sites with an occupancy ratio of 0.8:0.2.

Adducts of 1,4,8,11-tetraazacyclotetradecane with carboxylic acids: hydrogen-bonded supramolecular structures in two or three dimensions

2004 ◽  
Vol 60 (1) ◽  
pp. 65-75 ◽  
Author(s):  
Choudhury M. Zakaria ◽  
Alan J. Lough ◽  
George Ferguson ◽  
Christopher Glidewell
Keyword(s):  
Carboxylic Acid ◽  
Hydrogen Bonds ◽  
Water Molecule ◽  
Carboxylic Acids ◽  
Rotation Axis ◽  
Three Dimensional ◽  
Supramolecular Structures ◽  
Three Dimensions ◽  
Water Molecules ◽  
Two Dimensional

Four solvated salt-type adducts derived from cyclam (1,4,8,11-tetraazacyclotetradecane) and carboxylic acids have been structurally characterized. In the salt derived from adamantane-1-carboxylic acid, 4,11-diaza-1,8-diazoniacyclotetradecane bis(adamantane-1-carboxylate) tetrahydrate, (1) (monoclinic, P21/c, Z′ = 0.5), where the cation lies across a centre of inversion, the anions and the water molecules form chains of edge-fused R_4^2(8) and R_6^6(16) rings, which are linked into sheets by the cations. In the 4-aminobenzoate salt, 4,11-diaza-1,8-diazoniacyclotetradecane bis(4-aminobenzoate) monohydrate, (2) (monoclinic, C2/c, Z′ = 0.5), where the cation lies across a centre of inversion and the water molecule lies across a twofold rotation axis, the cations and anions generate a three-dimensional framework, readily analysed in terms of two distinct two-dimensional substructures, viz. (10\overline 1) sheets of R_8^6(46) rings, and pairwise interwoven (100) sheets, reinforced by water molecules. The 3-hydroxybenzoate salt, 4,11-diaza-1,8-diazoniacyclotetradecane bis(3-hydroxybenzoate) dihydrate, (3) (monoclinic, Pc, Z′ = 1), contains a three-dimensional framework constructed from anions and water molecules only, which encapsulates large voids and within which the cations are linked to the anion–water framework via N—H...O hydrogen bonds. There are two independent cations in 4,11-diaza-1,8-diazoniacyclotetradecane 5-hydroxyisophthalate(2−) methanol solvate, (4) (monoclinic, P21/c, Z′ = 1), both lying across centres of inversion but with entirely different configurations. The anions alone form simple chains, and these chains are linked by the two types of cation into a three-dimensional framework from which the methanol molecules are pendent. Comparisons are made with carboxylate complexes of the [Ni(cyclam)]2+ cation and with carboxylate salts derived from meso-5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane.

Transition Metal-Substituted Double Dawson-Type Polyoxotungstates and Their Supramolecular Structures

2010 ◽  
Vol 63 (1) ◽  
pp. 96 ◽  
Author(s):  
Shuang Yao ◽  
Zhiming Zhang ◽  
Yangguang Li ◽  
Enbo Wang
Keyword(s):  
Transition Metal ◽  
Electrocatalytic Activity ◽  
Supramolecular Structure ◽  
Metal Cations ◽  
Supramolecular Structures ◽  
Water Molecules ◽  
Supramolecular Architecture ◽  
Transition Metal Cations ◽  
One Dimensional ◽  
Lattice Water

Reactions of hexavacant polyoxotungstate [H2P2W12O48]12– ({P2W12}) with various transition metal cations lead to the isolation of three double Dawson-type polyoxotungstates: (C4H10NO)12Na2[α 1-MnP2W17O61]2·7H2O (1), [(CH3)2NH2]3K2Na11[α 1-CoP2W17O61]2·30H2O (2), and Na8K2[Fe2(H2O)8(Fe2P2W16O60)2]·41H2O (3). Compound 1 has a one-dimensional (1D) supramolecular architecture built from a Mn-substituted double Dawson-type polyoxoanion (DDTP) [α 1-MnP2W17O61]2 14–, morpholine, and lattice water molecules. Compound 2 has a 1D supramolecular structure built from the first Co-containing DDTP [α 1-CoP2W17O61]2 16– connected via H-bonding interactions. Compound 3 has a 3D supramolecular structure built from a Fe-substituted DDTP [Fe2(H2O)8(Fe2P2W16O60)2]10– and lattice water molecules. Electrocatalytic studies indicate that these three compounds all display electrocatalytic activity toward the reduction of nitrite.

Hydrated salts of 3,5-dihydroxybenzoic acid with organic diamines: hydrogen-bonded supramolecular structures in two and three dimensions

2001 ◽  
Vol 57 (3) ◽  
pp. 329-338 ◽  
Author(s):  
Colin J. Burchell ◽  
George Ferguson ◽  
Alan J. Lough ◽  
Richard M. Gregson ◽  
Christopher Glidewell
Keyword(s):  
Hydrogen Bonds ◽  
Three Dimensional ◽  
Supramolecular Structures ◽  
Three Dimensions ◽  
Acid Water ◽  
Water Molecules ◽  
Two Dimensional ◽  
Dihydroxybenzoic Acid ◽  
Hydrated Salt ◽  
Single Sheet

The trigonally trisubstituted acid 3,5-dihydroxybenzoic acid forms hydrated salt-type adducts with organic diamines. In 1,4-diazabicyclo[2.2.2]octane–3,5-dihydroxybenzoic acid–water (1/1/1) (1), where Z′ = 2 in P21/c, the constitution is [HN(CH2CH2)3N]+·[(HO)2C6H3COO]−·H2O: the anions and the water molecules are linked by six O—H...O hydrogen bonds to form two-dimensional sheets and each cation is linked to a single sheet by one O—H...N and one N—H...O hydrogen bond. Piperazine–3,5-dihydroxybenzoic acid–water (1/2/4) (2) and 1,2-diaminoethane–3,5-dihydroxybenzoic acid–water (1/2/2) (3) are also both salts with constitutions [H2N(CH2CH2)2NH2]2+·2[(HO)2C6H3COO]−·4H2O and [H3NCH2CH2NH3]2+·2[(HO)2C6H3COO]−·2H2O, respectively. Both (2) and (3) have supramolecular structures which are three-dimensional: in (2) the anions and the water molecules are linked by six O—H...O hydrogen bonds to form a three-dimensional framework enclosing large centrosymmetric voids, which contain the cations that are linked to the framework by two N—H...O hydrogen bonds; in (3) the construction of the three-dimensional framework requires the participation of cations, anions and water molecules, which are linked together by four O—H...O and three N—H...O hydrogen bonds.

Ferrocene-1,1′-dicarboxylic acid as a building block in supramolecular chemistry: supramolecular structures in one, two and three dimensions

2002 ◽  
Vol 58 (5) ◽  
pp. 786-802 ◽  
Author(s):  
Choudhury M. Zakaria ◽  
George Ferguson ◽  
Alan J. Lough ◽  
Christopher Glidewell
Keyword(s):  
Hydrogen Bonds ◽  
Dicarboxylic Acid ◽  
Three Dimensional ◽  
Two Dimensions ◽  
Supramolecular Structures ◽  
Three Dimensions ◽  
Two Dimensional ◽  
Acid Molecule ◽  
One Dimensional ◽  
Partial Transfer

The supramolecular structures have been determined for nine adducts formed between organic diamines and ferrocene-1,1′-dicarboxylic acid. In the salt-like 1:1 adduct (1) formed with methylamine, the supramolecular structure is one-dimensional, whereas in the 1:1 adducts formed with 1,4-diazabicyclo[2.2.2]octane, (2), and 4,4′-bipyridyl, (4), and in the hydrated 2:1 adduct (3) formed with morpholine, the hard hydrogen bonds form one-dimensional structures, which are expanded to two dimensions by soft C—H...O hydrogen bonds. The hard hydrogen bonds generate two-dimensional structures in the 2:1 adduct (5) formed with octylamine, where the ferrocene component lies across a centre of inversion, in the 1:1 adduct (6) formed with piperidine and in the tetrahydrofuran-solvated 1:1 adduct (7) formed with di(cyclohexyl)amine. In the 2:3 adduct (8) formed by tris-(2-aminoethyl)amine, and in the 2:1 adduct (9) formed with 2-(4′-hydroxyphenyl)ethylamine (tyramine), where Z′ = 1.5 in space group P\bar{1}, the hard hydrogen bonds generate three-dimensional structures. No H transfer from O to N occurs in (4) and only partial transfer of H occurs in (2); in (1), (6) and (7), one H is transferred to N from each acid molecule, and in (3), (5), (8) and (9), two H are transferred from each acid molecule.

The effect of partial methylation of the glycine amino group on crystal structure inN,N-dimethylglycine and its hemihydrate

2012 ◽  
Vol 68 (8) ◽  
pp. o283-o287 ◽  
Author(s):  
Vasily S. Minkov ◽  
Elena V. Boldyreva
Keyword(s):  
Crystal Structure ◽  
Hydrogen Bonds ◽  
Water Molecules ◽  
Amino Group ◽  
Asymmetric Unit ◽  
Partial Methylation ◽  
Space Groups ◽  
Carboxylate Groups ◽  
Anhydrous Compound ◽  
Additional Hydrogen

N,N-Dimethylglycine, C4H9NO2, and its hemihydrate, C4H9NO2·0.5H2O, are discussed in order to follow the effect of the methylation of the glycine amino group (and thus its ability to form several hydrogen bonds) on crystal structure, in particular on the possibility of the formation of hydrogen-bonded `head-to-tail' chains, which are typical for the crystal structures of amino acids and essential for considering amino acid crystals as mimics of peptide chains. Both compounds crystallize in centrosymmetric space groups (PbcaandC2/c, respectively) and have twoN,N-dimethylglycine zwitterions in the asymmetric unit. In the anhydrous compound, there are no head-to-tail chains but the zwitterions formR44(20) ring motifs, which are not bonded to each other by any hydrogen bonds. In contrast, in the crystal structure ofN,N-dimethylglycinium hemihydrate, the zwitterions are linked to each other by N—H...O hydrogen bonds into infiniteC22(10) head-to-tail chains, while the water molecules outside the chains provide additional hydrogen bonds to the carboxylate groups.

Hydrate von Li3VO4: Synthese und Strukturchemie / Hydrates of Li3VO4: Synthesis and Structural Chemistry

2007 ◽  
Vol 62 (10) ◽  
pp. 1235-1245 ◽  
Author(s):  
Simone Schnabel ◽  
Caroline Röhr
Keyword(s):  
Hydrogen Bonds ◽  
Building Blocks ◽  
Water Molecules ◽  
Space Group ◽  
Space Groups ◽  
Monoclinic Form ◽  
Lithium Sulfide ◽  
3D Network ◽  
Coordination Spheres ◽  
A Chain

Stoichiometric hydrates of Li3VO4, the hexahydrate and two polymorphs of the octahydrate, were prepared by evaporation of alkaline aqueous solutions 1 molar in LiOH and 0.5 molar in the metavanadate LiVO3 at r. t. with or without the addition of Lithium sulfide, i. e. at different pH values. Their crystal structures have been determined and refined using single crystal X-ray data; all lithium and hydrogen atom positions were localised and refined without contraints. All three title compounds crystallise in non-centrosymmetric space groups. The water molecules belong to the tetrahedral coordination spheres of the Li cations, i. e. they are embedded as water of coordination exclusively. The tetrahedral orthovanadate(V) anions VO3−4 and the LiO4 tetrahedra are connected via common O corners to form building units which are further held together by strong, nearly linear hydrogen bonds. The hexahydrate Li3VO4 ・ 6H2O (space group R3, a = 962.9(2), c = 869.2(2) pm, Z = 3, R1 = 0.0260) contains isolated orthovanadate(V) anions VO3−4 surrounded by a 3D network of cornersharing Li(H2O)4 tetrahedra forming rings of three, seven and eight units. The water molecules are ‘isolated’ in the sense that no hydrogen bonds are formed between water molecules. The octahydrate is dimorphous: The triclinic polymorph of Li3VO4 ・ 8H2O (space group P1, a = 592.6(2), b = 651.3(2), c = 730.2(4) pm, α = 89.09(2), β = 89.43(2), γ = 88.968(12)°, Z = 1, R1 = 0.0325) contains two types of chains of tetrahedra: One consists of corner-sharing Li(H2O)4 tetrahedra only, the second one is formed by alternating LiO4 and VO4 tetrahedra, also sharing oxygen corners. Only one water molecule is ‘isolated’, the other seven form a branched fragment of a chain with hydrogen bonds between them. In the monoclinic form of Li3VO4・8H2O (space group Pc, a = 732.6(1), b = 653.7(1), c = 1292.9(3) pm, β = 112.21(1)°, Z = 2, R1 = 0.0289) a fragment of a chain of three LiO4 tetrahedra, two of which share a common edge, and one VO4 tetrahedron represent the formular unit. These building blocks are connected via hydrogen bonds formed by three ‘isolated’ water molecules and a chain fragment of five connected water molecules.

scholarly journals Two New Polyiodides in the 4,4´-Bipyridinium Diiodide/Iodine System

2012 ◽  
Vol 67 (1) ◽  
pp. 5-10
Author(s):  
Guido J. Reiss ◽  
Martin van Megen
Keyword(s):  
Hydrogen Bonding ◽  
Hydrogen Bonds ◽  
Complex I ◽  
The Other ◽  
Cyclic Dimer ◽  
Water Molecules ◽  
Spectroscopic Methods ◽  
Halogen Bonds ◽  
One Dimensional ◽  
Hydroiodic Acid

The reaction of bipyridine with hydroiodic acid in the presence of iodine gave two new polyiodide-containing salts best described as 4,4´-bipyridinium bis(triiodide), C10H10N2[I3]2, 1, and bis(4,4´-bipyridinium) diiodide bis(triiodide) tris(diiodine) solvate dihydrate, (C10H10N2)2I2[I3]2 · 3 I2 ·2H2O, 2. Both compounds have been structurally characterized by crystallographic and spectroscopic methods (Raman and IR). Compound 1 is composed of I3 − anions forming one-dimensional polymers connected by interionic halogen bonds. These chains run along [101] with one crystallographically independent triiodide anion aligned and the other triiodide anion perpendicular to the chain direction. There are no classical hydrogen bonds present in 1. The structure of 2 consists of a complex I144− anion, 4,4´-bipyridinium dications and hydrogen-bonded water molecules in the ratio of 1 : 2 : 2. The I144− polyiodide anion is best described as an adduct of two iodide and two triiodide anions and three diiodine molecules. Two 4,4´-bipyridinium cations and two water molecules form a cyclic dimer through N-H· · ·O hydrogen bonds. Only weak hydrogen bonding is found between these cyclic dimers and the polyiodide anions.

Hydrogen Bonds in "Carboxyoximes": the Case of Bomane Derivatives

2000 ◽  
Vol 55 (8) ◽  
pp. 677-684 ◽  
Author(s):  
Maciej Kubicki ◽  
Teresa Borowiak ◽  
Wiesław Z. Antkowiak
Keyword(s):  
Carboxylic Acid ◽  
Hydrogen Bonds ◽  
Crystal Structures ◽  
Carboxylic Acids ◽  
Supramolecular Structures ◽  
X Ray Diffraction ◽  
X Ray ◽  
Carboxylic Groups ◽  
Acid Function

Abstract The tendency of forming mixed carboxyl-to-oxime hydrogen bonds was tested on the series of bornane derivatives: one with the acid function only (bornane-2-endo-carboxylic acid), one with the oxime function (2,2′-diethylthiobomane-3-oxime), and one with both oxime and carboxylic functions (bornane-2-oxime-3-endo-carboxylic acid). The crystal structures of these compounds were determined by means of X-ray diffraction. In bornane-2-endo-carboxylic acid and 2,2′-diethylthiobornane-3-oxime 'homogenic' hydrogen bonds were found, and these hydrogen bonds close eight-and six-membered rings, respectively. By contrast, in bornane-2-oxime-3-endo-carboxylic acid 'heterogenic' hydrogen bonds between carboxylic and oxime bonds were found. This carboxylic-oxime, or 'carboxyoxime' system is almost always present in compounds which have both oxime and carboxylic groups; therefore it can be regarded as an element of supramolecular structures (synthon). The presence of such synthons can break the tendency of carboxylic acids and oximes towards crystallizing in centrosymmetric structures.

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