scholarly journals Molecular Recognition in Proton-Transfer Compounds of Brucine with Achiral Substituted Salicylic Acid Analogues

2006 ◽  
Vol 59 (5) ◽  
pp. 320 ◽  
Author(s):  
Graham Smith ◽  
Urs D. Wermuth ◽  
Peter C. Healy ◽  
Jonathan M. White
Keyword(s):  
Proton Transfer ◽  
Three Dimensional ◽  
Water Molecules ◽  
Sulfosalicylic Acid ◽  
X Ray ◽  
X Ray Crystallography ◽  
Guest Species ◽  
Substituted Benzoic Acids ◽  
Proton Transfer Compounds ◽  
Hydrogen Bonded

The 1:1 proton-transfer brucinium compounds from the reaction of the alkaloid brucine with 5-nitrosalicylic acid, 3,5-dinitrosalicylic acid, and 5-sulfosalicylic acid, namely anhydrous brucinium 5-nitrosalicylate (1), brucinium 3,5-dinitrosalicylate monohydrate (2), and brucinium 5-sulfosalicylate trihydrate (3) have been prepared and their crystal structures determined by X-ray crystallography. All structures further demonstrate the selectivity of brucine for meta-substituted benzoic acids and comprise three-dimensional hydrogen-bonded framework polymers. Two of the compounds (1 and 3) have the previously described undulating brucine sheet host-substructures which incorporate interstitially hydrogen-bonded salicylate anion guest species and additionally in 3 the water molecules of solvation. The structure of 2 differs in having a three-centre brucinium–salicylate anion bidentate N+–H···O(carboxyl) hydrogen-bonding association linking the species through interstitial associations involving also the water molecules of solvation. A review of the crystallographic structural literature on strychnine and brucine is also given.

Inclusion Compounds of Thiourea and Peralkylated Ammonium Salts. VI. Hydrogen-Bonded Host Lattices Constructed From Thiourea and Anions of Oxalic Acid and Fumaric Acid

1997 ◽  
Vol 53 (2) ◽  
pp. 252-261 ◽  
Author(s):  
Q. Li ◽  
T. C. W. Mak
Keyword(s):  
Crystal Structure ◽  
Three Dimensional ◽  
Water Molecules ◽  
Space Group ◽  
X Ray ◽  
X Ray Crystallography ◽  
Single Column ◽  
Host Lattices ◽  
Type Crystal ◽  
Hydrogen Bonded

New inclusion complexes tetra-n-butylammonium hydrogen oxalate–thiourea (1/2), (n-C4H9)4N+.HC2O4 −.2[(NH2)2CS] (1), tetramethylammonium hydrogen fumarate–thiourea (1/1), (CH3)4N+.HC4H2O4 −.(NH2)2CS (2), di(tetraethylammonium) fumarate–thiourea (1/2), [(C2H5)4N+]2.C4H2O4 2−.2[(NH2)2CS] (3) and tetra-n-propylammonium hydrogen fumarate–thiourea–water (1/1/2), (n-C3H7)4N+.HC4H2 O4 −.(NH2)2CS.2H2O (4) have been prepared and characterized by X-ray crystallography. Crystal data, Mo Kα radiation: (1), space group P21/n, a = 8.854 (6), b = 9.992 (3), c = 32.04 (2) Å, β = 97.34 (3), Z = 4, R F = 0.055 for 2261 observed data; (2), space group P\overline 1, a = 6.269 (2), b = 8.118 (4), c = 14.562 (8) Å, α = 104.79 (4), β= 91.72 (4), γ = 101.30 (4)°, Z = 2, R F = 0.078 for 1543 observed data; (3), space group P21/n, a = 11.340 (2), b = 9.293 (6), c = 14.619 (2) Å, β = 102.41 (2)°, Z = 2, R F = 0.050 for 1856 observed data; (4), space group P2/n, a = 16.866 (4), b = 8.311  (1), c = 17.603 (2) Å, β = 104.94 (1)°, Z = 4, R F = 0.048 for 2785 observed data. In the crystal structure of (1) the tetra-n-butylammonium ions are sandwiched between puckered layers, which are constructed from thiourea-hydrogen oxalate ribbons. In the crystal structure of (2), zigzag O--H...O and C--H...O hydrogen-bonded hydrogen fumarate ribbons are linked by thiourea dimers to form a wide puckered ribbon and the crystal structure is built of a packing of these thiourea–anion composite ribbons and the cationic columns. In the layer-type crystal structure of (3) a series of thiourea–fumarate layers match the (002) planes and the (C2H5)4N+ cations occupy the intervening space. In the crystal structure of (4) the thiourea, hydrogen fumarate ions and water molecules are connected by hydrogen bonds to form wide puckered ribbons, which are crosslinked to generate a three-dimensional host framework containing open channels aligned parallel to the a axis, with the tetra-n-propylammonium cations accommodated in a single column within each channel.

Clathrates with Three-Dimensional Host Structures of Hydrogen-Bonded Pentaborate [B5O6(OH)4]- Ions: Pentaborates with the Cations NMe4+, NEt4+, NPhMe3+ and pipH+ (pipH+ = Piperidinium)

1993 ◽  
Vol 48 (7) ◽  
pp. 978-985 ◽  
Author(s):  
Michael Wiebcke ◽  
Clemens C. Freyhardt ◽  
Jürgen Felsche ◽  
Günter Engelhardt
Keyword(s):  
Rectangular Cross Section ◽  
Three Dimensional ◽  
Organic Cations ◽  
Water Molecules ◽  
Space Group ◽  
X Ray ◽  
Structure Topology ◽  
Guest Species ◽  
Gas Atmosphere ◽  
Hydrogen Bonded

X-ray structure analyses of crystalline [NMe4][B5O6(OH)4] · nH2O with n ≈ 0.25-0.50 (1), [NEt4][B5O6(OH)4] (2), [NPhMe3][B5O6(OH)4] (3), and [pipH][B5O6(OH)4] (4) reveal that these materials are novel clathrates with closely related three-dimensional host structures built up of hydrogen-bonded oligomeric pentaborate [B5O6(OH)4]- ions. The organic cations and water molecules (in 1) occupy as guest species large straight channel-like voids of nearly rectangular cross-section. Compound 1 crystallizes monoclinically with space group P2,/c (Z = 4); the compounds 2,3 and 4, which possess the same host-structure topology, crystallize triclinically with space group P1̄ (Z = 2). 11B-MAS NMR spectra allow the detection of small angular distortions in the pentaborate anions caused by the specific hydrogen bonding in the host frameworks. Upon heating the compounds on a thermobalance in a dynamic inert gas atmosphere dehydration occurs at temperatures of 563 K (1), 543 K (2), 558 K (3) and 523 K (4) before degradation of the organic cations starts at temperatures of 633 K (1), 623 K (2), 623 K (3) and 613 K (4).

Molecular tectonics — Use of urethanes and ureas derived from tetraphenylmethane and tetraphenylsilane to build porous chiral hydrogen-bonded networks

2004 ◽  
Vol 82 (2) ◽  
pp. 386-398 ◽  
Author(s):  
Dominic Laliberté ◽  
Thierry Maris ◽  
James D Wuest
Keyword(s):  
Hydrogen Bonding ◽  
Asymmetric Catalysis ◽  
Crystal Engineering ◽  
Three Dimensional ◽  
Enantiomerically Pure ◽  
X Ray ◽  
Molecular Tectonics ◽  
X Ray Crystallography ◽  
Open Networks ◽  
Hydrogen Bonded

Tetraphenylmethane, tetraphenylsilane, and simple derivatives with substituents that do not engage in hydrogen bonding typically crystallize as close-packed structures with essentially no space available for the inclusion of guests. In contrast, derivatives with hydrogen-bonding groups are known to favor the formation of open networks that include significant amounts of guests. To explore this phenomenon, we synthesized six new derivatives 5a–5e and 6a of tetraphenylmethane and tetraphenylsilane with urethane and urea groups at the para positions, crystallized the compounds, and determined their structures by X-ray crystallography. As expected, all six compounds crystallize to form porous three-dimensional hydrogen-bonded networks. In the case of tetraurea 5e, 66% of the volume of the crystals is accessible to guests, and guests can be exchanged in single crystals without loss of crystallinity. Of special note are: (i) the use of tetrakis(4-isocyanatophenyl)methane (1f) as a precursor for making enantiomerically pure tetraurethanes and tetraureas, including compounds 5b, 5c; and (ii) their subsequent crystallization to give porous chiral hydrogen-bonded networks. Such materials promise to include chiral guests enantioselectively and to be useful in the separation of racemates, asymmetric catalysis, and other applications.Key words: crystal engineering, molecular tectonics, hydrogen bonding, networks, porosity, urethanes, ureas, tetraphenylmethane, tetraphenylsilane.

Zweidimensionales Eis und H5O2+-Ionen. Zur Bildung und Struktur tiefschmelzender molekularer und ionischer Hemi-bis Hexahydrate halogenierter Essigsäuren CClnF3-nCOOH (n = 1 bis 3) [1] / Two-Dimensional Ice and H5O2+ Ions. On Formation and Structure of Low-Melting Molecular and Ionic Hemi-through Hexahydrates of Haloacetic Acids CClnF3-nCOOH (n = 1 to 3) [1]

1996 ◽  
Vol 51 (4) ◽  
pp. 536-544 ◽  
Author(s):  
Thomas Dahlems ◽  
Dietrich Mootz ◽  
Michaela Schilling
Keyword(s):  
Three Dimensional ◽  
Hydrate Formation ◽  
Molecular Structures ◽  
Haloacetic Acids ◽  
Water Molecules ◽  
Two Dimensional ◽  
Temperature Dependent ◽  
X Ray ◽  
Five Phases ◽  
Hydrogen Bonded

Abstract Hydrate formation of haloacetic acids CClnF3-nCOOH (n = 1, 2, 3) has been studied by DTA and temperature-dependent X-ray powder diffraction, and evidence obtained for five phases, all melting at temperatures below ambient. The hydrates have been confirmed and further characterized by their crystal structures at -150 °C. Three lower hydrates, CCl2FCOOH· 0.5H2O (space group P21/c and Z = 8 formula unites per unit cell), CClF2COOHH2O (P21/c, Z = 4), and CClF2COOH ·4H2O (P1̄, Z = 2), have molecular structures with the acid and water molecules hydrogen-bonded in two-dimensional arrays. The structures of the remaining hydrates, CCl2FCOOH·6H2O and CCl3COOH · 6H2O (similar, but not isotypic, both P1̄ and Z = 2), are ionic, as (H5O2+)(CX3COO-) · 4H2O , and three-dimensional. The neutral water molecules are hydrogen-bonded in ice-like layers rare in crystal chemistry. Also, CCl2FCOOH is established only as the second acid of which a lower hydrate is molecular and a higher one ionic.

scholarly journals Proton-transfer compounds featuring the unusual 4-arsonoanilinium cation from the reaction of (4-aminophenyl)arsonic acid with strong organic acids

2018 ◽  
Vol 233 (2) ◽  
pp. 145-151
Author(s):  
Graham Smith ◽  
Urs D. Wermuth
Keyword(s):  
Hydrogen Bonding ◽  
Proton Transfer ◽  
Organic Acids ◽  
Picric Acid ◽  
Three Dimensional ◽  
Water Molecules ◽  
Fold Axis ◽  
Arsanilic Acid ◽  
Arsonic Acid ◽  
Proton Transfer Compounds

AbstractThe crystal structures of the 1:1 proton-transfer compounds of (4-aminophenyl)arsonic acid (p-arsanilic acid) with the strong organic acids, 2,4,6-trinitrophenol (picric acid), 3,5-dinitrosalicylic acid, (3-carboxy-4-hydroxy)benzenesulfonic acid (5-sulfosalicylic acid) and toluene-4-sulfonic acid have been determined at 200 K and their hydrogen–bonding patterns examined. The compounds are, respectively, anhydrous 4-arsonoanilinium 2,4,6-trinitrophenolate (1), the hydrate 4-arsonoanilinium 2-carboxy-4,6-dinitrophenolate monohydrate (2), the hydrate 4-arsonoanilinium (3-carboxy-4-hydroxy)benzenesulfonate monohydrate (3) and the partial solvate 4-arsonoanilinium toluene-4-sulfonate 0.8 hydrate (4). The asymmetric unit of2, a phenolate, comprises two independent but conformationally similar cation-anion pairs and two water molecules of solvation, and in all compounds, extensive inter-species hydrogen–bonding interactions involving arsono O–H···O and anilinium N–H···O hydrogen–bonds generate three-dimensional supramolecular structures. In the cases of1and2, the acceptors include phenolate and nitro O-atom acceptors, with3and4, additionally, sulfonate O-atom acceptors, and with the hydrates2–4, the water molecules of solvation. A feature of the hydrogen–bonding in3is the presence of primary chains extending along (010) through centrosymmetric cyclicR22(8) motifs together with conjoined cyclicR34(12) motifs, which include the water molecule of solvation. The primary hydrogen–bonding in the substructure of4involves homomolecular cation–cation arsono O–H···O interactions forming columns down the crystallographic four-fold axis of the unit cell.

Hydrothermal synthesis, crystal structure and electrochemical properties of a novel 3D Dawson-type polyoxometalate supramolecular network

2008 ◽  
Vol 2008 (11) ◽  
pp. 626-629
Author(s):  
LiHong Tian ◽  
ShiZhong Liu ◽  
NingHai Hu ◽  
HengQing Jia
Keyword(s):  
Crystal Structure ◽  
Cyclic Voltammetry ◽  
Title Compound ◽  
Three Dimensional ◽  
Water Molecules ◽  
Supramolecular Network ◽  
Supramolecular Architecture ◽  
Single Crystal Diffraction ◽  
X Ray ◽  
X Ray Crystallography

A novel Dawson-type polyoxometalate supramolecular architecture of the formula [4,4′-H2bipy]2.5·[4,4′-Hbipy]·[P2W18O62]·6.25H2O (4,4′-bipy = 4,4′-bipyridine) has been hydrothermally synthesised and characterised by means of elemental analysis, IR, CV and X-ray single-crystal diffraction. X-ray crystallography indicates that the title compound consists of Dawson-type polyoxoaions [P2W18O62]6-, water molecules and 4,4′-bipy units. The polyoxoanion clusters together with 4,4′-bipy units and water molecules to construct the three-dimensional supramolecular network through hydrogen bonds. The crystal structure analyses reveal that water molecules and 4,4′-bipy units play the important role on the packing arrangements of crystals. Cyclic voltammetry shows that the title compound exhibits three chemically reversible steps

scholarly journals Crystal structures of 6-nitroquinazolin-4(3H)-one, 6-aminoquinazolin-4(3H)-one and 4-aminoquinazoline hemihydrochloride dihydrate

2021 ◽  
Vol 77 (10) ◽  
pp. 989-993
Author(s):  
Kambarali Turgunov ◽  
Mirjalol Ziyadullaev ◽  
Farkhod Khoshimov ◽  
Rikhsiboy Karimov ◽  
Burkhon Elmuradov
Keyword(s):  
Three Dimensional ◽  
Chloride Ion ◽  
Chloride Ions ◽  
Chloride Anion ◽  
Water Molecules ◽  
Asymmetric Unit ◽  
Amino Groups ◽  
X Ray ◽  
Dimensional Network ◽  
Hydrogen Bonded

The title compounds, 6-nitroquinazolin-4(3H)-one (C8H5N3O3; I), 6-aminoquinazolin-4(3H)-one (C8H7N3O; II) and 4-aminoquinazolin-1-ium chloride–4-aminoquinazoline–water (1/1/2), (C8H8N3 +·Cl−·C8H7N3·2H2O; III) were synthesized and their structures were determined by single-crystal X-ray analysis. In the crystals of I and II, the quinazoline molecules form hydrogen-bonded dimers via N—H...O interactions. The dimers are connected by weak intermolecular C—H...N and C—H...O hydrogen bonds, forming a layered structure in the case of I. In the crystal of II, N—H...N and C—H...O interactions link the dimers into a three-dimensional network structure. The asymmetric unit of III consists of two quinazoline molecules, one of which is protonated, a chloride ion, and two water molecules. The chloride anion and the water molecules form hydrogen-bonded chains consisting of fused five-membered rings. The protonated and unprotonated quinazolin molecules are linked to the chloride ions and water molecules of the chain by their amino groups.

Manifestations of noncovalent bonding in the solid state. 6. [H4(cyclam)]4+ (cyclam = 1,4,8,11-tetraazacyclotetradecane) as a template for crystal engineering of network hydrogen-bonded solids

1995 ◽  
Vol 73 (3) ◽  
pp. 414-424 ◽  
Author(s):  
S. Subramanian ◽  
Michael J. Zaworotko
Keyword(s):  
Hydrogen Bonding ◽  
Crystal Engineering ◽  
Water Molecules ◽  
Crystal Data ◽  
Large Excess ◽  
X Ray ◽  
X Ray Crystallography ◽  
Noncovalent Bonding ◽  
Perchlorate Salt ◽  
Hydrogen Bonded

A series of salts of composition [H4(cyclam)]X•nH2O, where cyclam = 1,4,8,11-tetraazacyclotetradecane and X = 4Cl− (1−, n = 4), 4Br− (2, n = 4), 4I− (3, n = x), 4ClO4−(4, n = 2), 4CNS− (5, n = 2), 2SO42−(6, n = 6), and (p-CH3C6H4SO3−) (7, n = 0) have been prepared and crystal structures of 1, 2, 4, 5, 6, and 7 have been determined by single crystal X-ray crystallography. 1, 2, 3, 4, and 7 were prepared by crystallizing cyclam with a large excess of the corresponding acid whereas the thiocyanate, 5, and the sulphate, 6, salts were prepared by metathesis of the perchlorate salt, 4, with KCNS and K2SO4, respectively. Crystal data: 1: orthorhombic, Pnnb, a = 7.7962(16), b = 14.278(4), c = 17.787(4) Å, V = 1979.9(8) Å3, Z = 4, Dc = 1.39 Mg m−3, Rf = 0.051, and Rw = 0.069 for 1176 reflections with I > 3σ(I). 2: triclinic. [Formula: see text]a = 7.6860(8), b = 7.8848(9), c = 9.6385(11) Å, α = 105.111(16)°, β = 95.495(18)°, γ = 102,464(17)°, V = 543.43(12) Å3, Z = 1, Dc = 1 1.82 Mg m−3,Rf = 0.034, and Rw = 0.041 for 1530 reflections with I > 3σ(I). 4: monoclinic, P21/n, a = 8.4519(11), b = 15.9248(12), c = 9.2981(17) Å, β = 106.243(18)°, V = 1201.5(3) Å3, Z = 2, Dc, = 1.76 Mg m−3, Rf = 0.052, and Rw = 0.068 for 1902 reflections with I > 3.0σ(I). 5: triclinic, [Formula: see text] a = 8.2996(7), b = 9.0061(15), c = 9.2015(15) Å, α = 107.60(3)°, β = 97.738(14)°, γ = 108.863(9)°, V = 599.44(15) Å3, Z = 1, Dc = 1.309 Mg m−3Rf = 0.038 and Rw = 0.049 for 1856 reflections with I > 4σ(I). 6: triclinic, [Formula: see text] a = 7.8687(5), b = 8.8396(12), c = 9.0405(25) Å, α = 68.547(16), β = 85.332(9), γ = 78.473(7)°, V = 573.43(18) Å3, Z = 1, Dc = 1.693 Mg m−3, Rf = 0.053 and Rw = 0.076 for 1441 reflections with I > 3σ(I). 7: triclinic, [Formula: see text] a = 8.533(3), b = 9.110(3), c = 15.3605(21) Å, α = 82.475(17)°, β = 74.307(20)°, γ = 73.26(3)°, V = 1099.0(5) Å3, Z = 1, Dc = 1.343 Mg m−3, Rf = 0.042 and Rw = 0.052 for 2460 reflections with I > 2.5σ(I). 1, 2, 4, 5, 6, and 7 exhibit extensive network hydrogen bonding between the anions, cations, and, if appropriate, water molecules of crystallization. The dimensionality of the hydrogen-bonded networks is dependent upon the nature of the anion and the number of water molecules of crystallization since the cation adapts a centrosymmetric exodentate conformation in all six salts. Keywords: crystal engineering, cyclams, network hydrogen bonding.

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