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.

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.

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.

scholarly journals Mechanochemical Synthesis and Structure of the Tetrahydrate and Mesoporous Anhydrous Metforminium(2+)-N,N’-1,4-Phenylenedioxalamic Acid Cocrystal Salt: The Role of Hydrogen Bonding and N→π* Charge Assisted Interactions

2020 ◽  
Author(s):  
Sayuri Chong-Canto ◽  
Efrén V. García-Báez ◽  
Francisco J. Martínez-Martínez ◽  
Ángel Ramos-Organillo ◽  
Itzia I. Padilla-Martínez
Keyword(s):  
Hydrogen Bonding ◽  
Mechanochemical Synthesis ◽  
Water Molecules ◽  
X Ray ◽  
X Ray Crystallography ◽  
Adsorption Desorption ◽  
First Time ◽  
Selective Formation ◽  
Crystallization From Solution

A new cocrystal salt of metformin, an antidiabetic drug, and N,N’-(1,4-phenylene)dioxalamic acid, was synthesized by mechanochemical synthesis, purified by crystallization from solution and characterized by single X-ray crystallography. The structure revealed a salt-type cocrystal composed of one dicationic metformin unit, two monoanionic units of the acid and four water molecules namely H2Mf(HpOXA)2∙4H2O. X-ray powder, IR, 13C-CPMAS, thermal and BET adsorption-desorption analyses were performed to elucidate the structure of the molecular and supramolecurar structure of the anhydrous microcrystalline mesoporous solid H2Mf(HpOXA)2. The results suggest that their structures, conformation and hydrogen bonding schemes are very similar between them. To the best of our knowledge, the selective formation of the monoanion HpOXA⁻, as well as its structure in the solid, is herein reported for the first time. Regular O(-)∙∙∙C(), O(-)∙∙∙N+ and bifacial O(-)∙∙∙C()∙∙∙O(-) of n→* charge-assisted interactions are herein described in H2MfA cocrystal salts which could be responsible of the interactions of metformin in biologic systems. The results, support the participation of n→* charge-assisted interactions independently, and not just as a short contact imposed by the geometric constraint due to the hydrogen bonding patterns.

Preparation of Rhenium Diamino Dithiolate Complexes. The X-Ray Crystal Structure of Oxo(1,1,8,8-tetraethyl-3,6-diazaoctane-1,8-dithiolato)rhenium

1993 ◽  
Vol 46 (7) ◽  
pp. 1093 ◽  
Author(s):  
TW Jackson ◽  
M Kojima ◽  
RM Lambrecht
Keyword(s):  
Crystal Structure ◽  
Hydrogen Bonding ◽  
Intermolecular Hydrogen Bonding ◽  
X Ray ◽  
X Ray Crystallography ◽  
Dithiolate Complexes ◽  
Hydrogen Bonded

The complexes oxo (1,1,8,8-tetraethyl-3,6-diazaoctane-1,8-dithiolato)rhenium[ ReO ( tedadt )], oxo (1,1,8,8-tetraethyl-4,4-dimethyl-3,6-diazaoctane-1,8-dithiolato)rhenium [ ReO ( tedmdadt )] and (1,1,4,4,8,8-hexamethyl-3,6-diazaoctane-1,8-dithiolato) oxorhenium [ ReO ( hmdadt )] were prepared. The crystal structure of the complex ReO ( tedadt ) was determined by X-ray crystallography to be a hydrogen-bonded dimer . This is the first example of intermolecular hydrogen bonding in rhenium diamino dithiolate ( dadt ) complexes.

Rage Against Conformity: Ruthenium(ɪɪ) Bisterpyridine Complexes Respond to Crystal Engineering Instructions with Whelming Results

2017 ◽  
Vol 70 (5) ◽  
pp. 529 ◽  
Author(s):  
Hasti Iranmanesh ◽  
Kasun S. A. Arachchige ◽  
William A. Donald ◽  
Niamh Kyriacou ◽  
Chao Shen ◽  
...  
Keyword(s):  
Hydrogen Bond ◽  
Hydrogen Bonding ◽  
Solid State ◽  
Single Crystal ◽  
Crystal Engineering ◽  
Intermolecular Hydrogen Bonding ◽  
Hydrogen Bond Donor ◽  
One Dimensional ◽  
X Ray ◽  
Hydrogen Bonded

Four heteroleptic ruthenium(ii) complexes of 4′-functionalised 2,2′:6′,2′′-terpyridine are reported, along with their solid-state single-crystal X-ray structures. The complexes feature complementary hydrogen-bond donor (phenol) and acceptor (pyridyl) groups designed to assemble into one-dimensional polymers. In one example, the system obeys the programmed instructions to form a one-dimensional, self-complementary hydrogen-bonded polymer. In one other example, a water-bridged hydrogen-bonded polymer is formed. In the remaining two structures, aryl–aryl interactions dominate the intermolecular interactions, and outweigh the contribution of intermolecular hydrogen bonding.

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.

Encapsulation of ferrocenes by hydrogen-bonded pyrogallol[4]arene dimers

2018 ◽  
Vol 73 (8) ◽  
pp. 597-600
Author(s):  
Bei Wang ◽  
Ai-Quan Jia ◽  
Hong-Mei Yang ◽  
Jing-Long Liu ◽  
Qian-Feng Zhang
Keyword(s):  
Hydrogen Bonding ◽  
Single Crystal ◽  
Molar Ratio ◽  
Reaction Conditions ◽  
X Ray ◽  
X Ray Crystallography ◽  
Capsule Type ◽  
Hydrogen Bonding Networks ◽  
Hydrogen Bonded

AbstractThe treatment of C-iso-butylpyrogallarene (PgC4) or C-ethylpyrogallarene (PgC2) with ferrocene (FcH) in a 2:1 molar ratio under different reaction conditions afforded the host–guest compounds FcH@(PgC4)2·CH3OH·3H2O (1) and FcH@(PgC2)2·3EtOH·2H2O (2), respectively. Complexes 1 and 2 are both pyrogallarene dimers providing capsule-type voids. Single crystal X-ray crystallography was used to investigate the role of hydrogen bonding networks in the assembly of the two host–guest systems.

Heterocyclic Tautomerism. IV. The Solution and Crystal Structures of 1-Aryl-3-phenyl-1,2,4-triazol-5-ones

1988 ◽  
Vol 41 (4) ◽  
pp. 419 ◽  
Author(s):  
AD Rae ◽  
CG Ramsay ◽  
PJ Steel
Keyword(s):  
Crystal Structure ◽  
Hydrogen Bonding ◽  
Solid State ◽  
Crystal Structures ◽  
Complex Network ◽  
Water Molecules ◽  
X Ray ◽  
Structure Determinations ◽  
Hydrogen Bonded

The title compounds are shown to exist in solution and in the solid state as 4H-tautomers. X-Ray crystal structure determinations show that 1,3-diphenyl-1,2,4-triazol-5-one exists as a dimeric pair of strongly hydrogen-bonded molecules and that 3-phenyl-1-(2-pyridyl)-1,2,4- triazol-5-one exists as the 4H-tautomer stabilized by a complex network of hydrogen bonding to water molecules.

Solid-state and gas-phase structures of two conformers of N-(4-methylphenyl)-N′,N′′-bis(morpholinyl) phosphoric triamide; insights from X-ray crystallography and DFT calculations

2011 ◽  
Vol 67 (3) ◽  
pp. 238-243 ◽  
Author(s):  
Khodayar Gholivand ◽  
Hamid Reza Mahzouni
Keyword(s):  
Hydrogen Bonding ◽  
Solid State ◽  
Dft Calculations ◽  
Gas Phase ◽  
Bond Critical Point ◽  
X Ray ◽  
X Ray Crystallography ◽  
Equal Chance ◽  
Phosphoric Triamide ◽  
Hydrogen Bonded

A phosphoric triamide with the formula (4-CH3—C6H4NH)P(O)(NC4H8O)2 has been synthesized and characterized. X-ray crystallography at 120 K reveals that the title compound is composed of two symmetrically independent molecules in the solid state. Density functional theory (DFT) calculations reveal that two conformers A and B are very close to each other from an energy point of view. Thus there is equal chance that the presence of two conformers in the lattice may lead to hydrogen-bonded chains with an ABABAB arrangement. Hydrogen bonds of the type OP...H—N (OP being the phosphoryl O atom) are established between the two conformers with binding energies of −18.8 and −20.3 kJ mol−1 (at B3LYP/6–31+G*). The electronic delocalization LP(OP) → σ*(N—H), LP(OP) being the lone pair of OP, leads to a decrease in the strength of the N—H bond during hydrogen bonding between the conformers. The charge density (ρ) at the bond critical point (b.c.p.) of N—H decreases by ∼ 0.012–0.014 e Å–3 when the molecule participates in hydrogen bonding. This may explain the red shift of the ν(N—H) stretching frequency from a single molecule in the gas phase to a hydrogen-bonded one in the solid state.

Concomitant polymorphs of 1,3-bis(3-fluorophenyl)urea

2016 ◽  
Vol 72 (9) ◽  
pp. 692-696 ◽  
Author(s):  
Christina A. Capacci-Daniel ◽  
Jeffery A. Bertke ◽  
Shoaleh Dehghan ◽  
Rupa Hiremath-Darji ◽  
Jennifer A. Swift
Keyword(s):  
Hydrogen Bonding ◽  
Crystal Engineering ◽  
Structural Motif ◽  
Parallel Orientation ◽  
One Dimensional ◽  
Monoclinic Form ◽  
Engineering Studies ◽  
Hydrogen Bonded

Hydrogen bonding between urea functionalities is a common structural motif employed in crystal-engineering studies. Crystallization of 1,3-bis(3-fluorophenyl)urea, C13H10F2N2O, from many solvents yielded concomitant mixtures of at least two polymorphs. In the monoclinic form, one-dimensional chains of hydrogen-bonded urea molecules align in an antiparallel orientation, as is typical of many diphenylureas. In the orthorhombic form, one-dimensional chains of hydrogen-bonded urea molecules have a parallel orientation rarely observed in symmetrically substituted diphenylureas.

Sign in / Sign up

Export Citation Format

Share Document