Three polymorphs of an inclusion compound of 2,2′-(disulfanediyl)dibenzoic acid and trimethylamine

2016 ◽  
Vol 72 (12) ◽  
pp. 981-989
Author(s):  
Yunxia Yang ◽  
Lihua Li ◽  
Li Zhang ◽  
Wenjing Dong ◽  
Keying Ding
Keyword(s):  
Hydrogen Bonds ◽  
Crystal Structures ◽  
Crystal Engineering ◽  
Inclusion Compound ◽  
Guest Molecule ◽  
Solid Material ◽  
Carboxyl Groups ◽  
Guest Molecules ◽  
Counter Ions ◽  
Host Lattices

Polymorphism is the ability of a solid material to exist in more than one form or crystal structure and this is of interest in the fields of crystal engineering and solid-state chemistry. 2,2′-(Disulfanediyl)dibenzoic acid (also called 2,2′-dithiosalicylic acid, DTSA) is able to form different hydrogen bonds using its carboxyl groups. The central bridging S atoms allow the two terminal arene rings to rotate freely to generate various hydrogen-bonded linking modes. DTSA can act as a potential host molecule with suitable guest molecules to develop new inclusion compounds. We report here the crystal structures of three new polymorphs of the inclusion compound of DTSA and trimethylamine, namely trimethylazanium 2-[(2-carboxyphenyl)disulfanyl]benzoate 2,2′-(disulfanediyl)dibenzoic acid monosolvate, C3H10N+·C14H9O4S2−·C14H10O4S2, (1), tetrakis(trimethylazanium) bis{2-[(2-carboxyphenyl)disulfanyl]benzoate} 2,2′-(disulfanediyl)dibenzoate 2,2′-(disulfanediyl)dibenzoic acid monosolvate, 4C3H10N+·2C14H9O4S2−·C14H8O4S22−·C14H10O4S2, (2), and trimethylazanium 2-[(2-carboxyphenyl)disulfanyl]benzoate, C3H10N+·C14H9O4S2−, (3). In the three polymorphs, DTSA utilizes its carboxyl groups to form conventional O—H...O hydrogen bonds to generate different host lattices. The central N atoms of the guest amine molecules accept H atoms from DTSA molecules to give the corresponding cations, which act as counter-ions to produce the stable crystal structuresviaN—H...O hydrogen bonding between the host acid and the guest molecule. It is noticeable that although these three compounds are composed of the same components, the final crystal structures are totally different due to the various configurations of the host acid, the number of guest molecules and the inducer (i.e.ancillary experimental acid).

scholarly journals Crystal structures of 2-aminopyridine citric acid salts: C5H7N2 +·C6H7O7 − and 3C5H7N2 +·C6H5O7 3−

2018 ◽  
Vol 74 (8) ◽  
pp. 1111-1116 ◽  
Author(s):  
Shet M. Prakash ◽  
S. Naveen ◽  
N. K. Lokanath ◽  
P. A. Suchetan ◽  
Ismail Warad
Keyword(s):  
Hydrogen Bond ◽  
Citric Acid ◽  
Hydrogen Bonds ◽  
Crystal Structures ◽  
Crystal Engineering ◽  
Molecular Conformation ◽  
Crystal Packing ◽  
Three Dimensional ◽  
Dimensional Structure ◽  
Almost All

2-Aminopyridine and citric acid mixed in 1:1 and 3:1 ratios in ethanol yielded crystals of two 2-aminopyridinium citrate salts, viz. C5H7N2 +·C6H7O7 − (I) (systematic name: 2-aminopyridin-1-ium 3-carboxy-2-carboxymethyl-2-hydroxypropanoate), and 3C5H7N2 +·C6H5O7 3− (II) [systematic name: tris(2-aminopyridin-1-ium) 2-hydroxypropane-1,2,3-tricarboxylate]. The supramolecular synthons present are analysed and their effect upon the crystal packing is presented in the context of crystal engineering. Salt I is formed by the protonation of the pyridine N atom and deprotonation of the central carboxylic group of citric acid, while in II all three carboxylic groups of the acid are deprotonated and the charges are compensated for by three 2-aminopyridinium cations. In both structures, a complex supramolecular three-dimensional architecture is formed. In I, the supramolecular aggregation results from Namino—H...Oacid, Oacid...H—Oacid, Oalcohol—H...Oacid, Namino—H...Oalcohol, Npy—H...Oalcohol and Car—H...Oacid interactions. The molecular conformation of the citrate ion (CA3−) in II is stabilized by an intramolecular Oalcohol—H...Oacid hydrogen bond that encloses an S(6) ring motif. The complex three-dimensional structure of II features Namino—H...Oacid, Npy—H...Oacid and several Car—H...Oacid hydrogen bonds. In the crystal of I, the common charge-assisted 2-aminopyridinium–carboxylate heterosynthon exhibited in many 2-aminopyridinium carboxylates is not observed, instead chains of N—H...O hydrogen bonds and hetero O—H...O dimers are formed. In the crystal of II, the 2-aminopyridinium–carboxylate heterosynthon is sustained, while hetero O—H...O dimers are not observed. The crystal structures of both salts display a variety of hydrogen bonds as almost all of the hydrogen-bond donors and acceptors present are involved in hydrogen bonding.

The formation of paracetamol (acetaminophen) adducts with hydrogen-bond acceptors

2002 ◽  
Vol 58 (6) ◽  
pp. 1057-1066 ◽  
Author(s):  
Iain D. H. Oswald ◽  
David R. Allan ◽  
Pamela A. McGregor ◽  
W. D. Samuel Motherwell ◽  
Simon Parsons ◽  
...  
Keyword(s):  
Hydrogen Bond ◽  
Crystal Structures ◽  
Systematic Study ◽  
Guest Molecule ◽  
Guest Molecules ◽  
Oh Groups ◽  
Stacking Interaction ◽  
Hydrogen Bond Interactions ◽  
Π Stacking Interaction ◽  
Graph Set

The crystal structures of five hemiadducts of paracetamol with 1,4-dioxane, N-methylmorpholine, morpholine, N,N-dimethylpiperazine and piperazine and a related 1:1 adduct of paracetamol with 4,4′-bipyridine are described. All structures are characterized by the formation of chains of paracetamol molecules, which are linked via either OH...O=C interactions [C(9) chains in graph-set notation] or NH...O=C interactions [C(4) chains], depending on the presence or absence of substituent groups on the guest molecule. In all cases except for the morpholine and bipyridine adducts these chains are connected by hydrogen-bond interactions with the guest molecules, which reside on crystallographic inversion centres. In the bipyridine adduct this linkage also involves a π-stacking interaction; in the morpholine adduct it is formed between the OH groups of two opposed paracetamol molecules. Most adducts (that with 4,4′-bipyridine is an exception) decompose on heating to give monoclinic paracetamol. This is the first systematic study of a series of co-crystals containing paracetamol.

Composite host lattices of 4,4′-sulfonyldibenzoate water/boric acid in two tetrapropylammonium inclusion compounds

2018 ◽  
Vol 74 (9) ◽  
pp. 1026-1031
Author(s):  
Xiangxiang Wu ◽  
Huahui Zeng ◽  
Yunxia Yang
Keyword(s):  
Boric Acid ◽  
Small Molecules ◽  
Crystal Structures ◽  
Inclusion Compounds ◽  
X Ray Diffraction ◽  
X Ray ◽  
Counter Ions ◽  
Proton Donors ◽  
The Difference ◽  
Host Lattices

Two novel inclusion compounds of 4,4′-sulfonyldibenzoate anions and tetrapropylammonium cations with different ancillary molecules of water and boric acid, namely bis(tetrapropylammonium) 4,4′-sulfonyldibenzoate dihydrate, 2C12H28N+·C14H8O6S2−·H2O (1), and bis(tetrapropylammonium) 4,4′-sulfonyldibenzoate bis(boric acid), 2C12H28N+·C14H8O6S2−·2H3BO3 (2), were prepared and characterized using single-crystal X-ray diffraction. In the two salts, the host 4,4′-sulfonyldibenzoic acid molecules, which are converted to the corresponding anions under basic conditions, can be regarded as proton acceptors which link different proton donors of the ancillary molecules of water or boric acid. In this way, an isolated hydrogen-bonded tetramer is constructed in salt 1 and a ribbon is constructed in salt 2. The tetramers and ribbons are then packed in a repeating manner to generate various host frameworks, and the tetrapropylammonium guest counter-ions are contained in the cavities of the host lattices to give the final stable crystal structures. In these two salts, although the host anion and guest cation are the same, the difference in the ancillary small molecules results in different structures, indicating the significance of ancillary molecules in the formation of crystal structures.

scholarly journals Construction of pillar[4]arene[1]quinone–1,10-dibromodecane pseudorotaxanes in solution and in the solid state

2020 ◽  
Vol 16 ◽  
pp. 2954-2959
Author(s):  
Xinru Sheng ◽  
Errui Li ◽  
Feihe Huang
Keyword(s):  
Solid State ◽  
Hydrogen Bonds ◽  
Single Crystal ◽  
Guest Molecule ◽  
X Ray Diffraction ◽  
Guest Molecules ◽  
X Ray ◽  
Π Interactions ◽  
Host Molecules ◽  
Complexation Stoichiometry

We report novel pseudorotaxanes based on the complexation between pillar[4]arene[1]quinone and 1,10-dibromodecane. The complexation is found to have a 1:1 host–guest complexation stoichiometry in chloroform but a 2:1 host–guest complexation stoichiometry in the solid state. From single crystal X-ray diffraction, the linear guest molecules thread into cyclic pillar[4]arene[1]quinone host molecules in the solid state, stabilized by CH∙∙∙π interactions and hydrogen bonds. The bromine atoms at the periphery of the guest molecule provide convenience for the further capping of the pseudorotaxanes to construct rotaxanes.

Systematic Structural Modification of a Pentacyclic Helical Tubuland Host Diol

1997 ◽  
Vol 50 (11) ◽  
pp. 1053 ◽  
Author(s):  
Paul D. Ahn, ◽  
Roger Bishop, ◽  
Donald C. Craig ◽  
Gary A. Downing ◽  
Marcia L. Scudder
Keyword(s):  
Hydrogen Bond ◽  
Hydrogen Bonds ◽  
Crystal Structures ◽  
Hydroxy Group ◽  
Network Structure ◽  
Crystal Engineering ◽  
Structural Modification ◽  
Dispersion Forces ◽  
Sectional Area ◽  
Space Group

Reaction of methylmagnesium chloride and pentacyclo[7.3.0.0 2,7.0 3,11 .0 6,10 ]dodecane-8,12-dione (4) yields the C2-symmetric diol (5) (62%) and the unsymmetrical diol (6) (36%) whose crystal structures are analysed in crystal engineering terms. The former isomer is the tenth member of the helical tubuland diol family, crystallizing in space groupP 3121 as a microporous lattice containing empty parallel canals with 9· 9Å2cross-sectional area. Molecules of diol (6) hydrogen bond through (-O-H)4 cycles to form layers which stack in space group P 21/c by means of hydrocarbon dispersion forces. Diol (7), the bis(trifluoromethyl) analogue of (5), does not form a helical tubuland lattice. The structure of its hemihydrate also contains (–O–H)4 cycles but here the second diol hydroxy group hydrogen bonds to water resulting in a network structure in space group P-421c.

Crystal Engineering Using Bisphenols and Trisphenols. Complexes with Hexamethylenetetramine (HMTA): Strings, Multiple Helices and Chains-of-Rings in the Crystal Structures of the Adducts of HTMA with 4,4'-Thiodiphenol (1/1), 4,4'-Sulfonyldiphenol (1/1), 4,4'-Isopropylidenediphenol (1/1), 1,1,1-Tris(4-hydroxyphenyl)ethane (1/2) and 1,3,5-Trihydroxybenzene (2/3)

1997 ◽  
Vol 53 (3) ◽  
pp. 521-533 ◽  
Author(s):  
P. I. Coupar ◽  
C. Glidewell ◽  
G. Ferguson
Keyword(s):  
Hydrogen Bonding ◽  
Hydrogen Bonds ◽  
Crystal Structures ◽  
Crystal Engineering ◽  
Triple Helix ◽  
Structural Motif ◽  
Rotation Axes ◽  
Double Helices ◽  
Graph Set ◽  
A Chain

The 4,4′-bisphenols (1), X(C6H4OH)2 [a, X = nil; b, X = O; c, X = S; d, X = 502; e, X = CO; f, X = CH2; g, X = CMe2; h, X = C(CF3)2], when co-crystallized from alcoholic solutions with hexamethylenetetramine, (CH2)6N4 (HMTA), form 1:1 adducts (4a)–(h). 4,4′-Thiodiphenol–hexamethylenetetramine (1/1), (4c), C12H10O2S.C6H12N4, and 4,4′- sulfonyldiphenol–hexamethylenetetramine (1/1), (4d), C12H10O4S.C6H12N4, are orthorhombic, Pmn21, (4c) a = 15.029 (2), b = 9.7954 (8), c = 5.9817 (11) Å and (4d) a = 14.779 (2), b = 10.2558 (15), c = 5.9817 (8) Å, with Z = 2, and the structures consist of zigzag chains comprising strings of alternating bisphenol and HMTA units, each lying across mirror planes and linked by O—H...N hydrogen bonds. In addition, both (4c) and (4d) exhibit C—H...\pi(arene) hydrogen bonds with one CH2 group of the HMTA unit acting as a donor to two different arene rings; (4d) also exhibits multiple C—H...O=S hydrogen bonds with three C—H bonds in each HMTA unit acting as donors towards a single sulfone O atom. 4,4′-Isopropylidenediphenol–hexamethylenetetramine (1/1), (4g), C15H16O2.C6H12N4, is monoclinic, C2/c, a = 25.093 (6), b = 7.1742 (13), c = 23.612 (7) Å, \beta = 110.42 (2)°, with Z = 8, and again the structure is built from chains of alternating bisphenol and HMTA units linked by O—H...N hydrogen bonds, but these now form double helices around twofold rotation axes; the double helices are themselves linked into sheets by C—H...O hydrogen bonds. The trisphenol (2), CH3C(C6H4OH)3, forms three adducts (5a)–(c) with HMTA, having trisphenol:HMTA ratios of 1:2 (5a), 2:3 (5b) and 1:1 (5c). 1,1,1-Tris(4-hydroxyphenyl)ethane–hexamethylenetetramine (1/2), (5a), C20H18O3.(C6H12N4)2, is orthorhombic, P212121, a = 6.9928 (10), b = 14.0949 (15), c = 30.999 (4) Å, with Z = 4, and the trisphenol units and half the HMTA units form a triple helix around a 21 axis, in which each strand consists of alternating phenol and HMTA units, linked as usual by O—H...N hydrogen bonds. The remaining HMTA units, which are external to the triple helix, are connected to it by O—H...N hydrogen bonds and are formed into externally buttressing stacks. The triol (3), 1,3,5-C6H3(OH)3, forms a 2:3 adduct (6) with HMTA. 1,3,5-Trihydroxybenzene–hexamethylenetetramine (2/3), (6), C6H6O3.(C6H12N4)1.5, is monoclinic, C2/c, a = 23.598 (2), b = 7.136 (2), c = 19.445 (3) Å, \beta = 96.822 (11)°, with Z = 8, and the dominant structural motif consists of centrosymmetric rings containing two molecules each of (3) and HMTA, connected by O—H...N hydrogen bonds; these rings are themselves linked into a chain-of-rings by further HMTA units lying on twofold rotation axes. The hydrogen-bonding patterns are codified using the graph-set approach.

Diversity of N-triphenylacetyl-L-tyrosine solvates with halogenated solvents

2021 ◽  
Vol 77 (12) ◽  
Author(s):  
Agnieszka Czapik ◽  
Marcin Kwit
Keyword(s):  
Hydrogen Bonds ◽  
Crystal Structures ◽  
Free Form ◽  
X Ray Diffraction ◽  
Scanning Calorimetry ◽  
Intermolecular Hydrogen Bonds ◽  
Guest Molecules ◽  
Sterically Demanding ◽  
Halogenated Solvents ◽  
Solvent Molecules

The structure of N-triphenylacetyl-L-tyrosine (C29H25NO4, L-TrCOTyr) is characterized by the presence of both donors and acceptors of classical hydrogen bonds. At the same time, the molecule contains a sterically demanding and hydrophobic trityl group capable of participating in π-electron interactions. Due to its large volume, the trityl group may favour the formation of structural voids in the crystals, which can be filled with guest molecules. In this article, we present the crystal structures of a series of N-triphenylacetyl-L-tyrosine solvates with chloroform, namely, L-TrCOTyr·CHCl3 (I) and L-TrCOTyr·1.5CHCl3 (III), and dichloromethane, namely, L-TrCOTyr·CH2Cl2 (II) and L-TrCOTyr·0.1CH2Cl2 (IV). To complement the topic, we also decided to use the racemic amide N-triphenylacetyl-DL-tyrosine (rac-TrCOTyr) and recrystallized it from a mixture of chloroform and dichloromethane. As a result, rac-TrCOTyr·1.5CHCl3 (V) was obtained. In the crystal structures, the amide molecules interact with each other via O—H...O hydrogen bonds. Noticeably, the amide N—H group does not participate in the formation of intermolecular hydrogen bonds. Channels are formed between the TrCOTyr molecules and these are filled with solvent molecules. Additionally, in the crystals of III and V, there are structural voids that are occupied by chloroform molecules. Structure analysis has shown that solvates I and II are isostructural. Upon loss of solvent, the solvates transform into the solvent-free form of TrCOTyr, as confirmed by thermogravimetric analysis, differential scanning calorimetry and powder X-ray diffraction.

scholarly journals Formation of quinol co-crystals with hydrogen-bond acceptors

2005 ◽  
Vol 61 (1) ◽  
pp. 46-57 ◽  
Author(s):  
Iain D. H. Oswald ◽  
W. D. Samuel Motherwell ◽  
Simon Parsons
Keyword(s):  
Hydrogen Bond ◽  
Hydrogen Bonding ◽  
Crystal Structures ◽  
Guest Molecule ◽  
Crystal Packing ◽  
Strong Hydrogen Bond ◽  
Hydrogen Bond Acceptor ◽  
Guest Molecules ◽  
Sterically Hindered

The crystal structures of eight new co-crystals of quinol with pyrazine, piperazine, morpholine, pyridine, piperidine, 4,4′-bipyridine, N-methylmorpholine and N,N′-dimethylpiperazine are reported. Quinol forms 1:1 co-crystals with pyrazine, piperazine and N,N′-dimethylpiperazine, but 1:2 co-crystals with morpholine, 4,4′-bipyridine, N-methylmorpholine, pyridine and piperidine. This difference can be rationalized in most cases by the presence of, respectively, two or one strong hydrogen-bond acceptor(s) in the guest molecule. The exception to this generalization is 4,4′-bipyridine, which forms a 1:2 co-crystal, possibly to optimize crystal packing. All structures are dominated by hydrogen bonding between quinol and the guest molecules. A doubly bridging motif, which connects pairs of quinol and guest molecules via NH...O or CH...O interactions, is present in all but the sterically hindered N,N′-dimethylpiperazine and N-methylmorpholine co-crystals.

The protonation of the ethylenediphosphinetetraacetate anion and the crystal structure of the bis (hydrogen bromide) of ethylenediphosphinetetraacetic acid

1981 ◽  
Vol 46 (12) ◽  
pp. 3063-3073 ◽  
Author(s):  
Jana Podlahová ◽  
Bohumil Kratochvíl ◽  
Vratislav Langer ◽  
Josef Šilha ◽  
Jaroslav Podlaha
Keyword(s):  
Crystal Structure ◽  
Hydrogen Bonds ◽  
Structure Determination ◽  
Free Acid ◽  
Hydrogen Bromide ◽  
Carboxyl Groups ◽  
Spectroscopic Methods ◽  
X Ray ◽  
Partial Formation

The equilibria and mechanism of addition of protons to the ethylenediphosphinetetraacetate anion (L4-) were studied in solution by the UV, IR, 1H and 31P NMR spectroscopic methods. A total of six protons can be bonded to the anion. They are added stepwise, first with partial formation of zwitterions containing P-H bonds, which then dissociate with formation of the free acid, H4L, where all four protons are bonded in carboxyl groups. The formation of zwitterions is strongly dependent on the concentration. In the final stage, the acid bonds two additional protons to form the bis-phosphonium cation, H6L2+. A number of isostructural salts containing this cation, H4L.2 HX (X = Cl, Br, I), have been prepared. The X-ray crystal structure determination of the bromide confirmed the expected arrangement. The bromide crystals are monoclinic, a = 578.2, b = 1 425.0, c = 1 046.7 pm, β = 103.07° with a space group of P21/c, Z = 2. The final R factor was 0.059 based on 1 109 observed reflections. The structure consists of H6L2+ cations containing protons bonded to phosphorus atoms (P-H distance 134 pm) and of bromide anions, located in gaps which are also sufficiently large for I- anions in the isostructural iodide. The interbonding of phosphonium cations proceeds through hydrogen bonds, C-OH...O=C, in which the O...O distance is 275.3 pm.

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