Polysulfonylamine, CLIII [1]. Schwache Wasserstoffbrücken mit aktivierten Methyldonoren: Kristallstrukturen von Cholinium-, Betainium- und Dimethyl[2-(dimethylamino)ethyl]ammonium-dimesylamid Polysulfonylamines, CLIII [1]. Weak Hydrogen Bonding with Activated Methyl Donors: Crystal Structures of Cholinium, Betainium and Dimethyl[2-(dimethylamino)ethyl]ammonium-dimesylamide

In order to study weak hydrogen bonds originating from inductively activated C(sp3)-H donor groups, low-temperature X-ray structures are reported for three onium salts of general formula BH+(MeSO2)2N-, where BH+ is Me3N+CH2CH2OH (1; orthorhombic, space group P212121, Z′ = 1), Me3N+CH2C(O)OH (2; orthorhombic, P212121, Z′ = 1), or Me2HN+CH2CH2NMe2 (3; monoclinic, P21/c, Z′ = 1). The asymmetric units consist of cationanion pairs assembled by an O-H···O=S hydrogen bond in 1, an O-H···N- bond in 2, and an N+-H ··· N- bond in 3. The packings display a plethora of short interionic C(sp3)-H···O/N contacts that are geometrically consistent with weak hydrogen bonding; those taken into consideration have normalized parameters d(H ··· O) ≤ 269 pm, d(H···N) ≤ 257 pm and θ(C-H···O/N) ≥ 127°. The roles of the weak hydrogen bonds are as follows: In structures 1 and 3, the anions are associated into corrugated layers, which intercalate catemers of cations (1) or stacks of discrete cations (3), whereas structure 2 involves cation catemers surrounded by four anion catemers and vice versa; moreover, all cations are linked to adjacent anions by several weak hydrogen bonds (and to one anion in particular by the strong H bond). Among the cation-anion interactions, the N+(CH2-H···)3O tripod pattern arising in 1 and 2 is of special interest.

Download Full-text

Polysulfonylamine, CLI [1]. Starke und schwache Wasserstoffbrücken in den Kristallstrukturen von 8-Hydroxychinolinium- und 8-Aminochinolinium-dimesylamid / Polysulfonylamines, CLI [1]. Strong and Weak Hydrogen Bonding in the Crystal Structures of 8-Hydroxyquinolinium and 8-Aminoquinolinium Dimesylamide

Zeitschrift für Naturforschung B ◽

10.1515/znb-2002-0509 ◽

2002 ◽

Vol 57 (5) ◽

pp. 524-533

Author(s):

Dagmar Henschel ◽

Oliver Moers ◽

Karna Wijaya ◽

Armand Blaschette ◽

Peter G. Jones

Keyword(s):

Hydrogen Bonding ◽

Hydrogen Bonds ◽

Monoclinic Space Group ◽

Organic Crystals ◽

Onium Salts ◽

Weak Hydrogen Bonds ◽

Weak Hydrogen Bonding ◽

Normalized Parameters ◽

Simple Chain ◽

Polymeric Structures

In order to study hydrogen bonding networks and packing arrangements in ionic organic crystals, low-temperature X-ray structures were determined for two chemically related onium salts BH+(MeSO2)2ND, where BH+ is 8-hydroxyquinolinium (1; monoclinic, space group P21/ c, Z´ = 1) or 8-aminoquinolinium (2; monoclinic, P21/n, Z´ = 1). The packings are governed by strong hydrogen bonds, π-π stacking interactions and weak hydrogen bonding. In both compounds, hydrogen bonds using the NH/OH donors of the cations and O/N acceptors of the anion result in simple chain polymeric structures, which extend parallel to the y axis and are propagated by translation (1) or 21 transformation (2). Moreover, an intramolecular N- H···O hydrogen bond is present in the 8-hydroxyquinolinium cation. As a common feature, the anion substructures are pervaded by hexagonal channels parallel to y, each one accommodating either two separate stacks of translation related cations (1) or a unique (merged) stack of inversion related cations (2). The crystal cohesion is reinforced by numerous weak hydrogen bonds of the types Car-H···O=S and CH2-H···O=S, the latter creating in each structure a topologically different double-chain ribbon of anions. All C-H···O contacts taken into consideration have normalized parameters d(H···O) ≤ 268 pm and θ(CDH···O) ≥ 126°.

Download Full-text

Polysulfonylamine, CXLII [1]. Ein supramolekulares Monomer-Dimer-Paar: Starke und schwache Wasserstoffbrücken in den Kristallstrukturen von Pyridinium-dimesylamid und 4,4´-Bipyridindiium-bis(dimesylamid) / Polysulfonylamines, CXLII [1]. A Supramolecular Monomer-Dimer Pair: Strong and Weak Hydrogen Bonding in the Crystal Structures of Pyridinium Dimesylamide and 4,4´-Bipyridinediium Bis(dimesylamide)

Zeitschrift für Naturforschung B ◽

10.1515/znb-2001-1013 ◽

2001 ◽

Vol 56 (10) ◽

pp. 1041-1051 ◽

Cited By ~ 2

Author(s):

Oliver Moers ◽

Ilona Lange ◽

Karna Wijaya ◽

Armand Blaschette ◽

Peter G. Jones

Keyword(s):

Hydrogen Bond ◽

Hydrogen Bonding ◽

Low Temperature ◽

Hydrogen Bonds ◽

Crystal Structures ◽

Strong Hydrogen Bond ◽

Orthorhombic Space Group ◽

X Ray ◽

Normalized Parameters ◽

Hydrogen Bonding Networks

In order to study packing arrangements and hydrogen bonding networks, low-temperature X-ray structures were determined for pyH+(MeSO2)2N- (M, orthorhombic, space group P212121, Z′ = 1) and 4,4′-bipyH22+ ·(MeSO2)2N- (D, monoclinic, C2/c, Z′ = 0.5). The structures consist of ionic formula entities assembled by N+-H···N- hydrogen bonds; the dication in D displays crystallographic C2 symmetry and has its two pyridyl moieties twisted by 43.9°. According to the packing architectures, D represents a supramolecular dimer of the monomeric congener M. In particular, the (MeSO2)2N- ions of the M structure are associated via short C(sp3) - H···O contacts to form a diamondoid network, whereas in D a topologically congruent framework is constructed from weakly hydrogen-bonded [(MeSO2)N-]2 nodes. Hexagonal channels in the anion substructures each include two adjacent stacks of monomeric pyH+ or “dimeric” 4,4-bipyH22+ cations that are linked to the channel walls by the strong hydrogen bond(s) and a set of short Car-H···O contacts. All C - H···O taken into consideration have normalized parameters d(H···O) ≤ 270 pm and θ(C - H···O) ≥ 115°.

Download Full-text

Polysulfonylamine, CLV [1]. Starke und schwache Wasserstoffbrücken in den Kristallstrukturen von 2,2΄-Bipyridinium-, 1,10-Phenanthrolinium- und 1,8-Bis(dimethylamino)naphthalinium-dimesylamid / Polysulfonylamines, CLV [1]. Strong and Weak Hydrogen Bonding in the Crystal Structures of 2,2΄-Bipyridinium, 1,10-Phenanthrolinium and 1,8-Bis(dimethylamino)naphthalinium Dimesylamide

Zeitschrift für Naturforschung B ◽

10.1515/znb-2002-0710 ◽

2002 ◽

Vol 57 (7) ◽

pp. 777-790 ◽

Cited By ~ 5

Author(s):

Dagmar Henschel ◽

Oliver Moers ◽

Ilona Lange ◽

Armand Blaschette ◽

Peter G Jones

Keyword(s):

Hydrogen Bond ◽

Hydrogen Bonding ◽

Low Temperature ◽

Hydrogen Bonds ◽

Salient Feature ◽

Monoclinic Space Group ◽

Proton Sponge ◽

X Ray ◽

Organic Bases ◽

Weak Hydrogen Bonding

As a sequel to prior reports on strong and weak hydrogen bonding in onium di(methanesulfonyl) amide crystals, low-temperature X-ray structures are described for three salts of general formula BH+(MeSO2)2N-, where BH+ is 2,2΄-bipyridinium (1; monoclinic, space group P21/n, Z΄ = 1), 1,10-phenanthrolinium (2; monoclinic, P21/c, Z΄ = 2), or 1,8-bis(dimethylamino) naphthalinium (3; orthorhombic, P212121, Z΄ = 1). Monoprotonation of the organic bases by (MeSO2)2NH results in the formation of an intra-cation N-H···N hydrogen bond, which is asymmetric in 1 and 2, but approximately symmetric in the proton-sponge cation of 3. Moreover, the acidic H atom is engaged in a cation-anion contact N-H···N- in 1 and 2 or H+···Oδ- in 3, thus conferring three-centre character upon the strong hydrogen bonding. Each structure displays a multitude of close interionic C-H···O/N contacts that are geometrically consistent with weak hydrogen bonding. A salient feature is provided by short S-CH2-H···O-S inter-anion contacts, which lead to layers in 1 and to catemers in 2, but are non-existent in structure 3. The cations of both 1 and 2 form π-stacks that are intercalated between the anion layers or surrounded by six anion catemers, whereas in structure 3 each cation is octahedrally coordinated by six anions and vice-versa. The heteroionic connectivity comprises the aforementioned branches of the strong three-centre hydrogen bonds (in 1-3), numerous Car-H···A bonds (1, 2: A = O; 3: A = O, N), S-CH2-H···Nring interactions (1, 2), and close N-CH2-H···O=S contacts (3; possibly destabilizing).

Download Full-text

Polysulfonylamine, CXLIII [1], Rolle schwacher Wasserstoffbrücken (C - H···O) in den Kristallstrukturen von 2,6-Dimethylpyridinium-, 1-Hydroxypyridinium- und Imidazolium-dimesylamid / Polysulfonylamines, CXLIII [1], Role of Weak Hydrogen Bonds (C - H···O) in the Crystal Structures of 2,6-Dimethylpyridinium , 1-Hydroxypyridinium and Imidazolium Dimesylamide

Zeitschrift für Naturforschung B ◽

10.1515/znb-2001-1014 ◽

2001 ◽

Vol 56 (10) ◽

pp. 1052-1062 ◽

Cited By ~ 6

Author(s):

Oliver Moers ◽

Karna Wijaya ◽

Thomas Hamann ◽

Armand Blaschette ◽

Peter G. Jones

Keyword(s):

Hydrogen Bonds ◽

Three Dimensional ◽

Strong Hydrogen Bond ◽

Monoclinic Space Group ◽

X Ray ◽

Onium Salts ◽

Weak Hydrogen Bonds ◽

Normalized Parameters ◽

Imidazolium Ion

In order to study hydrogen bonding networks in ionic crystals, low-temperature X-ray structures were determined for three onium salts of general formula BH+(MeSO2)2N- , where BH+ is 2,6-dimethylpyridinium (1; monoclinic, space group P21/c, Z′ = 1), 1-hydroxypyridinium (2; triclinic, P1̅, Z′ = 1), or imidazolium (3; monoclinic, Cc, Z′ = 1). The asymmetric units consist of cation-anion pairs assembled in 1 and 3 by ordinary N+ - H···N hydrogen bonds, in 2 by a very short N+ - O - H···N- bond belonging to the class (+/-)CAHB [H···O 148(3), O···N 253.5(2) pm, O - H···N 175(3)°]. The second N -H donor of the imidazolium ion is involved in a nearly symmetric N - H (···O)2 three-centre bond to two different anions. In the pyridine derivatives, the (MeSO2 )2N- ions are associated via short C(sp3) - H···O contacts to form a three-dimensional framework of corrugated and cross-linked layers (1) or an assembly of discrete corrugated layers (2). As a common feature, these anion substructures are pervaded by hexagonal channels parallel to x, each one accommodating two stacks of cations that are linked to the channel walls by the unique strong hydrogen bond and a set of short Car - H···O contacts; moreover, cations drawn from adjacent stacks in structure 2 create inversion-symmetric dimers based upon a short Car - H···O(H) - N interaction. In contrast, the structure of 3 displays planar anion layers assembled by short C(sp3 ) - H···O contacts, intercalating the cations with their ring planes perpendicular to the layer planes and binding them by means of the strong hydrogen bonds and three Car -H···O interactions. All C - H···O taken into consideration have normalized parameters d( H···O) ≤ 267 pm and θ(C - H···O) ≥ 121°.

Download Full-text

Polysulfonylamine, CXVII Wasserstoffbrücken in kristallinen Onium-dimesylamiden: Sechs systematisch variierte sek.-Ammonium-dimesylamide mit sechs verschiedenen null-, ein-oder zweidimensionalen Wasserstoffbrückenmustern/ Polysulfonylamines, CXVII Hydrogen Bonding in Crystalline Onium Dimesylamides: Six Systematically Varied sec. - Ammonium Dimesylamides Exhibiting Six Different Zero-, One-, or Two-Dimensional Hydrogen Bonding Patterns

Zeitschrift für Naturforschung B ◽

10.1515/znb-1999-1115 ◽

1999 ◽

Vol 54 (11) ◽

pp. 1420-1430 ◽

Cited By ~ 4

Author(s):

Oliver Moers ◽

Karna Wijaya ◽

Dagmar Henschel ◽

Armand Blaschette ◽

Peter G. Jones

Keyword(s):

Hydrogen Bond ◽

Hydrogen Bonding ◽

Hydrogen Bonds ◽

Ionic Crystals ◽

Molecular Fragments ◽

Triclinic Space Group ◽

X Ray ◽

Rigid Conformation ◽

Morpholinium Salt ◽

Crystal Packings

In order to examine packing preferences and hydrogen bond patterns in secondary ammonium salts, low-temperature X-ray analyses were conducted for six compounds of general formula R2NH2+MeSO2)2 N-, where R2NH2+ = Me2NH2+ (1, triclinic, space group P1̄̄), MeEtNH2+,(2, monoclinic, P21/c), Et2NH2+ (3. triclinic, P1), pyrrolidinium (4, triclinic, P1), piperidinium (5, monoclinic, C2/c) or morpholinium (6, monoclinic, P21/c). Throughout the series, the constant anion retains a rigid conformation approximating to C2 symmetry and thus provides a geometrically reliable set of five potential hydrogen bond acceptors. Nevertheless, the six compounds exhibit a variety of unpredictable packing patterns, showing that, in unfavourable cases, the steric demands of molecular fragments not involved in hydrogen bonding can substantially alter the structure of a family of ionic crystals. In the present structures, the NH2+ donor groups form hydrogen bonds N+-H···N-/O to two (3-6) or three (1,2) adjacent anions. The occurrence of various two-, three- and four-centre hydrogen bonds leads to six different patterns, resulting in cation-anion layers (1, 2), discrete formula unit dimers (3, 4) or cation-anion chains (5, 6); in the morpholinium salt 6, these chains are associated into layers by a weak N+ - H ··· O(cation) interaction. In each of the crystal packings, short C-H···O contacts with H···O ≤ 270 pm and C-H ···O ≥ 130° are observed.

Download Full-text

Correspondence: Hydrogen Bond to Gold? 1H NMR is Not a Proof of Hydrogen Bonds in Transition Metal Complexes

10.26434/chemrxiv.7460714.v1 ◽

2018 ◽

Cited By ~ 2

Author(s):

Jan Vícha ◽

Cina Foroutan-Nejad ◽

Michal Straka

Keyword(s):

Hydrogen Bond ◽

Hydrogen Bonding ◽

Hydrogen Bonds ◽

Chemical Shifts ◽

X Ray ◽

Structure And Dynamics ◽

Hydrogen Bonding Interactions ◽

Overall Stability ◽

Gold Compounds ◽

C Nmr

Illusive AuI/III···H hydrogen bonds and their effect on structure and dynamics of molecules have been a matter of debate. While a number of X-ray studies reported gold compounds with short AuI/III···H contacts, a solid spectroscopic evidence for AuI/III···H bonding has been missing. Recently<a></a><a>, Bakar et al.</a> (NATURE COMMUNICATIONS 8:576) reported compound with four short Au···H contacts (2.61–2.66 Å; X-ray determined). Assuming the central cluster be [Au6]2+and observing the 1H (13C) NMR resonances at relevant H(C) nuclei deshielded with respect to precursor compound, the authors concluded with reservations that “the present Au···H–C interaction is a kind of “hydrogen bond”, where the [Au6]2+serves as an acceptor”. Here, we show that the Au6cluster in their compound bears negative charge and the Au···H contacts lead to a weak (~1 kcal/mol) auride···hydrogen bonding interactions, though unimportant for the overall stability ofthe molecule. Additionally, computational analysis of NMR chemical shifts reveals that the deshielding effects at respective hydrogen nuclei are not directly related to Au···H–C hydrogen bonding .

Download Full-text

Unusual hydrogen bonding inL-cysteine hydrogen fluoride

Acta Crystallographica Section C Structural Chemistry ◽

10.1107/s2053229615013601 ◽

2015 ◽

Vol 71 (8) ◽

pp. 733-741

Author(s):

V. S. Minkov ◽

V. V. Ghazaryan ◽

E. V. Boldyreva ◽

A. M. Petrosyan

Keyword(s):

Hydrogen Bond ◽

Hydrogen Bonding ◽

Hydrogen Bonds ◽

Hydrogen Fluoride ◽

Fluoride Ion ◽

X Ray Diffraction ◽

Monoclinic System ◽

X Ray ◽

Short Hydrogen Bond ◽

Doubly Charged

L-Cysteine hydrogen fluoride, or bis(L-cysteinium) difluoride–L-cysteine–hydrogen fluoride (1/1/1), 2C3H8NO2S+·2F−·C3H7NO2S·HF or L-Cys+(L-Cys...L-Cys+)F−(F−...H—F), provides the first example of a structure with cations of the `triglycine sulfate' type,i.e.A+(A...A+) (whereAandA+are the zwitterionic and cationic states of an amino acid, respectively), without a doubly charged counter-ion. The salt crystallizes in the monoclinic system with the space groupP21. The dimeric (L-Cys...L-Cys+) cation and the dimeric (F−...H—F) anion are formedviastrong O—H...O or F—H...F hydrogen bonds, respectively, with very short O...O [2.4438 (19) Å] and F...F distances [2.2676 (17) Å]. The F...F distance is significantly shorter than in solid hydrogen fluoride. Additionally, there is another very short hydrogen bond, of O—H...F type, formed by a L-cysteinium cation and a fluoride ion. The corresponding O...F distance of 2.3412 (19) Å seems to be the shortest among O—H...F and F—H...O hydrogen bonds known to date. The single-crystal X-ray diffraction study was complemented by IR spectroscopy. Of special interest was the spectral region of vibrations related to the above-mentioned hydrogen bonds.

Download Full-text

Structure in “Amorphous Regions”, Accessible Segments of Fibrils, of the Cotton Fiber

Textile Research Journal ◽

10.1177/004051758805800204 ◽

1988 ◽

Vol 58 (2) ◽

pp. 96-101 ◽

Cited By ~ 11

Author(s):

Stanley P. Rowland ◽

Phyllis S. Howley

Keyword(s):

Hydrogen Bond ◽

Hydrogen Bonding ◽

Hydrogen Bonds ◽

Cotton Fiber ◽

Cotton Fibers ◽

X Ray Diffraction ◽

X Ray ◽

Chemical Studies

The extent of hydrogen bonding of O(3)H and O(6)H in “amorphous” regions, more specifically in accessible segments of fibrils, of the cotton fiber varied from near perfection to almost complete disorder in samples under examination. Perfection of hydrogen bonding in various samples and segments of cotton fibers decreased with decreasing crystallinity of the cellulose within the fibrils. For the most part, extents of O(3)H hydrogen bonding and O(6)H hydrogen bonding followed similar patterns with substantial differences in degrees of perfection, the O(3)H ranging from about 95% hydrogen bonding down to 8% and the O(6)H) from 92% down to 41%. Details of hydrogen bonds assessed in these chemical studies are discussed relative to crystallinities and assignments of hydrogen bond structures from x-ray diffraction studies.

Download Full-text

Correspondence: Hydrogen Bond to Gold? 1H NMR is Not a Proof of Hydrogen Bonds in Transition Metal Complexes

10.26434/chemrxiv.7460714 ◽

2018 ◽

Author(s):

Jan Vícha ◽

Cina Foroutan-Nejad ◽

Michal Straka

Keyword(s):

Hydrogen Bond ◽

Hydrogen Bonding ◽

Hydrogen Bonds ◽

Chemical Shifts ◽

X Ray ◽

Structure And Dynamics ◽

Hydrogen Bonding Interactions ◽

Overall Stability ◽

Gold Compounds ◽

C Nmr

Download Full-text

On hydrogen bonding in 1,6-anhydro-β-D-glucopyranose (levoglucosan): X-ray and neutron diffraction and DFT study

Acta Crystallographica Section B Structural Science ◽

10.1107/s010876810602489x ◽

2006 ◽

Vol 62 (5) ◽

pp. 912-918 ◽

Cited By ~ 19

Author(s):

Ľubomír Smrčok ◽

Mariana Sládkovičová ◽

Vratislav Langer ◽

Chick C. Wilson ◽

Miroslav Koóš

Keyword(s):

Hydrogen Bond ◽

Hydrogen Bonding ◽

Solid State ◽

Hydrogen Bonds ◽

Neutron Diffraction ◽

Dft Calculations ◽

Diffraction Data ◽

Neutron Diffraction Study ◽

Single Crystal Diffraction ◽

X Ray

The geometry of hydrogen bonds in 1,6-anhydro-β-D-glucopyranose (levoglucosan) is accurately determined by refinement of time-of-flight neutron single-crystal diffraction data. Molecules of levoglucosan are held together by a hydrogen-bond array formed by a combination of strong O—H...O and supporting weaker C—H...O bonds. These are fully and accurately detailed by the neutron diffraction study. The strong hydrogen bonds link molecules in finite chains, with hydroxyl O atoms acting as both donors and acceptors of hydroxyl H atoms. A comparison of molecular and solid-state DFT calculations predicts red shifts of O—H and associated blue shifts of C—H stretching frequencies due to the formation of hydrogen bonds in this system.

Download Full-text