Crystal chemistry of tetraradial species. Part 9. The versatile BPh4- anion, or how organoammonium H(N) atoms compete for hydrogen bonding

1998 ◽  
Vol 76 (5) ◽  
pp. 583-611 ◽  
Author(s):  
Katherine N Robertson ◽  
Pradip K Bakshi ◽  
Susanne D Lantos ◽  
T Stanley Cameron ◽  
Osvald Knop
Keyword(s):  
Hydrogen Bonding ◽  
Crystal Structures ◽  
Solvent Molecule ◽  
Proton Sponge ◽  
Bond Forming ◽  
Steric Accessibility ◽  
Bicyclic Diamines ◽  
Proton Sponges ◽  
The Many ◽  
Considerable Detail

In organoammonium cations containing two or more N atoms, the H(N) atom introduced by the protonation may engage in an N→H(N)...Y bond to an external acceptor (anion or solvent molecule); in an intra-cation (intra-annular) N→H(N)...N' bond; or in a branched N→H(N)...N',Y bond(s), simultaneously intra-cation and to one or more external acceptors. The outcome of the competition for these bond types is determined by various factors, e.g., the size of the ring to be closed by insertion of the H(N) atom, steric accessibility of H(N), and the H-bond-forming strength of Y. Some of these are discussed in considerable detail and are exemplified by the hitherto unreported crystal structures of the tetraphenylborates (solvated or unsolvated) of the 2,2':6',2"-terpyridinium (1), 2,3-bis(2-pyridyl)pyrazinium (2), 2,2'-dipyridylammonium (3), 6,7-dihydro[b,j][1,10]phenanthrolinium (9), 2,4,7-triamino-6-pteridinium (triamterenium, 10), proton-sponge (1-Me2N-8-Me2NH-naphthalene, 11, 12), and 9-amino-1,2,3,4-tetrahydroacridinium (tacrinium, 13) cations. The crystal structures of the comparison compounds 2,3-bis(2-pyridyl)pyrazine (4) and its mono- (2A) and diprotonated (3) chlorides, and of 2-phenylpyridinium (6) and 7,8-benzoquinolinium (7, 8) tetraphenylborates, have also been determined. The many interesting features of these crystal structures, such as the X→H(X)...phenyl bonding (X = N, O, C), are commented upon and crystallographic comparisons with numerous literature compounds are offered. Included in the discussion are the monoprotonated intrabridgehead cations of the bicyclic diamines of Alder et al., the N-H(N)-N' angle of which has been shown, analytically, to be dominated by the size of the smallest of the rings in these tricyclic systems.Key words: crystal structures, hydrogen bonding, intrabridgehead cations, proton sponges, tetraphenylborates.

Crystal chemistry of tetraradial species. Part 8. Mix and match: cation geometry, ion packing, hydrogen bonding, and π–π interactions in cis-2,2′-bipyridinium(1+) and 1,10-phenanthrolinium(1+) tetraphenylborates — and what about proton sponges?

1996 ◽  
Vol 74 (2) ◽  
pp. 201-220 ◽  
Author(s):  
Pradip K. Bakshi ◽  
T. Stanley Cameron ◽  
Osvald Knop
Keyword(s):  
Hydrogen Bonding ◽  
Detailed Comparison ◽  
Spectroscopic Properties ◽  
Stacking Interactions ◽  
Proton Sponge ◽  
Bonding Interaction ◽  
Proton Sponges ◽  
In Cis ◽  
Considerable Detail ◽  
Mix And Match

The crystal structures at −20 °C of cis-2,2′-bipyridinium(1+) (BPTB, P21/n, a = 9.249(3), b = 14.093(7), c = 20.285(3) Å, β = 92.86(2)°, Z = 4) and 1,10-phenanthrolinium(1+) (PTB, P21/c, a = 11.194(2), b = 13.837(3), c = 18.303(3) Å, β = 107.82(1)°, Z = 4) tetraphenylborates have been determined. Inasmuch as 1,10-phenanthroline is an aromatically bridged cis-2,2′-bipyridine, monoprotonation results, in both systems, in the formation of an intra-cation N—H … N′ hydrogen bond, the geometric and spectroscopic properties of which we have investigated. The cation skeleton in PTB is planar to 0.03(2) Å; in BPTB the dihedral angle between the two cation ring planes is 5.2°. In the pale yellow PTB there are significant π–π stacking interactions that persist into solution. The effect of protonation on the geometry of the 2,2′-bipyridine and 1,10-phenanthroline systems is examined in considerable detail and compared with the corresponding effects in the paraquat(2+) and similar cations. On both geometric and spectroscopic (infrared spectra between 10 and 295 K) evidence, the N—H … N′ hydrogen-bonding interaction is stronger in BPTB; in PTB this interaction is among the weakest reported in crystals, the ν(NH) stretching frequency at 10 K being as high as 3279 cm−1. A detailed comparison of the geometries of the intra-cation N—H … N′ bonds in BPTB and PTB with those in classical and modified proton-sponge cations has led to the formulation of criteria useful in predicting the occurrence of proton-sponge-like properties. Key words: bipyridinium ions, hydrogen bonding, phenanthrolinium ions, proton sponges, tetraphenylborates.

Two terphenyl-based diol hosts and corresponding solvent inclusions with dimethylformamide and acetonitrile

2015 ◽  
Vol 71 (9) ◽  
pp. 768-775
Author(s):  
Hendrik Klien ◽  
Wilhelm Seichter ◽  
Konstantinos Skobridis ◽  
Edwin Weber
Keyword(s):  
Hydrogen Bonding ◽  
Crystal Structures ◽  
Solvent Molecule ◽  
Intramolecular Hydrogen Bonding ◽  
Host Lattice ◽  
Solvent Free ◽  
Guest Molecules ◽  
Solvent Molecules ◽  
Intramolecular Hydrogen ◽  
Supramolecular Aggregates

Having reference to an elongated structural modification of 2,2′-bis(hydroxydiphenylmethyl)biphenyl, (I), the two 1,1′:4′,1′′-terphenyl-based diol hosts 2,2′′-bis(hydroxydiphenylmethyl)-1,1′:4′,1′′-terphenyl, C44H34O2, (II), and 2,2′′-bis[hydroxybis(4-methylphenyl)methyl]-1,1′:4′,1′′-terphenyl, C48H42O2, (III), have been synthesized and studied with regard to their crystal structures involving different inclusions,i.e.(II) with dimethylformamide (DMF), C44H34O2·C2H6NO, denoted (IIa), (III) with DMF, C48H42O2·C2H6NO, denoted (IIIa), and (III) with acetonitrile, C48H42O2·CH3CN, denoted (IIIb). In the solvent-free crystals of (II) and (III), the hydroxy H atoms are involved in intramolecular O—H...π hydrogen bonding, with the central arene ring of the terphenyl unit acting as an acceptor. The corresponding crystal structures are stabilized by intermolecular C—H...π contacts. Due to the distinctive acceptor character of the included DMF solvent species in the crystal structures of (IIa) and (IIIa), the guest molecule is coordinated to the hostviaO—H...O=C hydrogen bonding. In both crystal structures, infinite strands composed of alternating host and guest molecules represent the basic supramolecular aggregates. Within a given strand, the O atom of the solvent molecule acts as a bifurcated acceptor. Similar to the solvent-free cases, the hydroxy H atoms in inclusion structure (IIIb) are involved in intramolecular hydrogen bonding, and there is thus a lack of host–guest interaction. As a result, the solvent molecules are accommodated as C—H...N hydrogen-bonded inversion-symmetric dimers in the channel-like voids of the host lattice.

Structural similarities among eight benzoylhydrazones

2014 ◽  
Vol 70 (9) ◽  
pp. 912-919
Author(s):  
Quoc Cuong Ton ◽  
Michael Bolte ◽  
Ernst Egert
Keyword(s):  
Crystal Structure ◽  
Hydrogen Bonding ◽  
Hydrogen Bonds ◽  
Crystal Structures ◽  
Phenyl Ring ◽  
Molecular Conformation ◽  
Solvent Molecule ◽  
Amide Group ◽  
Benzoyl Group ◽  
Independent Molecules

The crystal structures of eight benzoylhydrazones with different substituents have been investigated, namely 1-benzoyl-2-(propan-2-ylidene)hydrazone, C10H12N2O, (I), 1-benzoyl-2-(1-cyclohexylethylidene)hydrazone, C15H20N2O, (II), 1-benzoyl-2-[1-(naphthalen-2-yl)ethylidene]hydrazone, C19H16N2O, (III), 1-benzoyl-2-(1-cyclohexylbenzylidene)hydrazone, C20H22N2O, (IV), 1-benzoyl-2-(1-phenylbenzylidene)hydrazone, C20H16N2O, (V), 1-benzoyl-2-[1-(4-chlorophenyl)benzylidene]hydrazone, C20H15ClN2O, (VI), 1-benzoyl-2-(4-hydroxybenzylidene)hydrazone methanol monosolvate, C14H12N2O2·CH3OH, (VII), and 1-benzoyl-2-(1,1-diphenylpropan-2-ylidene)hydrazone, C22H20N2O, (VIII). The ten molecules in the eight crystal structures [there are two independent molecules in the structures of (V) and (VI)] show similar conformations and hydrogen-bonding patterns. The C=N—NH—C=O group is planar, but the plane of the phenyl ring of the benzoyl group is rotated by about 30° with respect to that of the keto group [except for (IV), where the groups are coplanar]. Only in the amide group of (VIII) is the N—H groupsynto the C=O bond, whereas the seven other compounds exhibit theanticonformation. Unless prevented by steric hindrance, N—H...O hydrogen bonds help to stabilize the crystal structure, which leads to infinite chains or dimers depending upon the molecular conformation. The molecular packing is supported by intermolecular C—H...O interactions. In the crystal structure of (VII), the methanol solvent molecule participates in two strong hydrogen bonds and two weak C—H...O interactions, thus acting as a link between the molecular chains.

scholarly journals Crystal structures and supramolecular features of 9,9-dimethyl-3,7-diazabicyclo[3.3.1]nonane-2,4,6,8-tetraone, 3,7-diazaspiro[bicyclo[3.3.1]nonane-9,1′-cyclopentane]-2,4,6,8-tetraone and 9-methyl-9-phenyl-3,7-diazabicyclo[3.3.1]nonane-2,4,6,8-tetraone dimethylformamide monosolvate

2017 ◽  
Vol 73 (7) ◽  
pp. 1097-1101 ◽  
Author(s):  
Sergey Z. Vatsadze ◽  
Marina A. Manaenkova ◽  
Evgeny V. Vasilev ◽  
Nikolai U. Venskovsky ◽  
Victor N. Khrustalev
Keyword(s):  
Hydrogen Bond ◽  
Hydrogen Bonding ◽  
Hydrogen Bonds ◽  
Crystal Structures ◽  
Dihedral Angle ◽  
Mirror Symmetry ◽  
Solvent Molecule ◽  
Twofold Axis ◽  
The Mean ◽  
Methyl Analog

Compounds (I), C9H10N2O4, (II), C11H12N2O4, and (III), C14H12N2O4·C3H7NO represent 9,9-disubstituted-3,7-diazabicyclo[3.3.1]nonane-2,4,6,8-tetraone derivatives with very similar molecular geometries for the bicyclic framework: the dihedral angle between the planes of the imide groups is 74.87 (6), 73.86 (3) and 74.83 (6)° in (I)–(III), respectively. The dimethyl derivative (I) is positioned on a crystallographic twofold axis and its overall geometry deviates only slightly from idealizedC2vsymmetry. The spiro-cyclopentane derivative (II) and the phenyl/methyl analog (III) retain only internalCssymmetry, which in the case of (II) coincides with crystallographic mirror symmetry. The cyclopentane moiety in (II) adopts an envelope conformation, with the spiro C atom deviating from the mean plane of the rest of the ring by 0.548 (2) Å. In compound (III), an N—H...O hydrogen bond is formed with the dimethylformamide solvent molecule. In the crystal, both (I) and (II) form similar zigzag hydrogen-bonded ribbons through double intermolecular N—H...O hydrogen bonds. However, whereas in (I) the ribbons are formed by twotrans-arranged O=C—N—H amide fragments, the amide fragments arecis-positioned in (II). The formation of ribbons in (III) is apparently disrupted by participation of one of its N—H groups in hydrogen bonding with the solvent molecule. As a result, the molecules of (III) form zigzag chains rather than the ribbons through intermolecular N—H...O hydrogen bonds. The crystal of (I) was a pseudo-merohedral twin.

scholarly journals Crystal structures offac-tricarbonylchlorido(6,6′-dihydroxy-2,2′-bipyridine)rhenium(I) tetrahydrofuran monosolvate andfac-bromidotricarbonyl(6,6′-dihydroxy-2,2′-bipyridine)manganese(I) tetrahydrofuran monosolvate

2016 ◽  
Vol 72 (8) ◽  
pp. 1201-1205
Author(s):  
Sheri Lense ◽  
Nicholas A. Piro ◽  
Scott W. Kassel ◽  
Andrew Wildish ◽  
Brent Jeffery
Keyword(s):  
Hydrogen Bonding ◽  
Crystal Structures ◽  
Hydroxy Group ◽  
Metal Ion ◽  
Solvent Molecule ◽  
Intramolecular Hydrogen Bonding ◽  
Distorted Octahedral Geometry ◽  
Halide Ligand ◽  
Bipyridine Ligand ◽  
Intramolecular Hydrogen

The structures of two facially coordinated Group VII metal complexes,fac-[ReCl(C10H8N2O2)(CO)3]·C4H8O (I·THF) andfac-[MnBr(C10H8N2O2)(CO)3]·C4H8O (II·THF), are reported. In both complexes, the metal ion is coordinated by three carbonyl ligands, a halide ligand, and a 6,6′-dihydroxy-2,2′-bipyridine ligand in a distorted octahedral geometry. Both complexes co-crystallize with a non-coordinating tetrahydrofuran (THF) solvent molecule and exhibit intermolecular but not intramolecular hydrogen bonding. In both crystal structures, chains of complexes are formed due to intermolecular hydrogen bonding between a hydroxy group from the 6,6′-dihydroxy-2,2′-bipyridine ligand and the halide ligand from a neighboring complex. The THF molecule is hydrogen bonded to the remaining hydroxy group.

scholarly journals The crystal structures and mechanical properties of the uranyl carbonate minerals roubaultite, fontanite, sharpite, widenmannite, grimselite and čejkaite

2020 ◽  
Vol 7 (21) ◽  
pp. 4197-4221 ◽  
Author(s):  
Francisco Colmenero ◽  
Jakub Plášil ◽  
Jiří Sejkora
Keyword(s):  
Mechanical Properties ◽  
Hydrogen Bonding ◽  
Diffraction Pattern ◽  
Crystal Structures ◽  
First Principles ◽  
X Ray Diffraction ◽  
Carbonate Minerals ◽  
X Ray ◽  
Uranyl Carbonate

The structure, hydrogen bonding, X-ray diffraction pattern and mechanical properties of six important uranyl carbonate minerals, roubaultite, fontanite, sharpite, widenmannite, grimselite and čejkaite, are determined using first principles methods.

Cobalt(II) aldoxime complexes stabilised by halide hydrogen bonding: crystal structures of [Co{HONC(H)(Me)}4X2] (X = Cl or Br) and [Co{HONC(H)(Pr)}4Cl2]

2001 ◽  
pp. 197-201 ◽  
Author(s):  
Jean-Cyrille Hierso ◽  
Elisabeth Bouwman ◽  
Dianne D. Ellis ◽  
Mónica Pérez Cabero ◽  
Jan Reedijk ◽  
...  
Keyword(s):  
Hydrogen Bonding ◽  
Crystal Structures

Rietveld refinement of the cocrystal 2,4-dihydroxybenzoic acid–N′-(propan-2-ylidene)nicotinohydrazide (1/1)

2012 ◽  
Vol 68 (9) ◽  
pp. o335-o337 ◽  
Author(s):  
Saul H. Lapidus ◽  
Andreas Lemmerer ◽  
Joel Bernstein ◽  
Peter W. Stephens
Keyword(s):  
Hydrogen Bond ◽  
Hydrogen Bonding ◽  
Powder Diffraction ◽  
Supramolecular Assembly ◽  
Covalent Bond ◽  
Analytical Tool ◽  
Powder Diffraction Data ◽  
Dihydroxybenzoic Acid ◽  
Bond Forming ◽  
Hydrogen Bond Interactions

A further example of using a covalent-bond-forming reaction to alter supramolecular assembly by modification of hydrogen-bonding possibilities is presented. This concept was introduced by Lemmerer, Bernstein & Kahlenberg [CrystEngComm(2011),13, 55–59]. The title structure, C9H11N3O·C7H6O4, which consists of a reacted niazid molecule,viz.N′-(propan-2-ylidene)nicotinohydrazide, and 2,4-dihydroxybenzoic acid, was solved from powder diffraction data using simulated annealing. The results further demonstrate the relevance and utility of powder diffraction as an analytical tool in the study of cocrystals and their hydrogen-bond interactions.

Supramolecular assembling using synthons with NH—CO(S)—CS—NH and NH—CO—CO—NH functionalities: crystal structures of (S,S)-N,N′-monothiooxalyldileucine methyl ester and its dithio analogue

2004 ◽  
Vol 60 (1) ◽  
pp. 90-96 ◽  
Author(s):  
Biserka Kojić-Prodić ◽  
Berislav Perić ◽  
Zoran Štefanić ◽  
Anton Meden ◽  
Janja Makarević ◽  
...  
Keyword(s):  
Hydrogen Bond ◽  
Hydrogen Bonding ◽  
Methyl Ester ◽  
Crystal Structures ◽  
Hydrogen Bond Network ◽  
Asymmetric Unit ◽  
Orthorhombic Space Group ◽  
Space Group ◽  
Bond Network ◽  
Bonding Systems

To compare the structural properties of oxalamide and thiooxalamide groups in the formation of hydrogen bonds suitable for supramolecular assemblies a series of retropeptides was studied. Some of them, having oxalamide bridges, are gelators of organic solvents and water. However, retropeptides with oxygen replaced by the sp 2 sulfur have not exhibited such properties. The crystal structures of the two title compounds are homostructural, i.e. they have similar packing arrangements. The monothio compound crystallizes in the orthorhombic space group P212121 with two molecules in the asymmetric unit arranged in a hydrogen-bond network with an approximate 41 axis along the crystallographic b axis. However, the dithio and dioxo analogues crystallize in the tetragonal space group P41 with similar packing patterns and hydrogen-bonding systems arranged in agreement with a crystallographic 41 axis. Thus, these two analogues are isostructural having closely related hydrogen-bonding patterns in spite of the different size and polarity of oxygen and sulfur which serve as the proton acceptors.

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