Crystal Engineering of Stacked Aromatic Columns. Three-Dimensional Control of the Alignment of Orthogonal Aromatic Triads and Guest Quinones via Self-Assembly of Hydrogen-Bonded Networks

1996 ◽  
Vol 118 (24) ◽  
pp. 5562-5571 ◽  
Author(s):  
Yasuhiro Aoyama ◽  
Ken Endo ◽  
Takashi Anzai ◽  
Yuji Yamaguchi ◽  
Tomoya Sawaki ◽  
...  
Keyword(s):  
Crystal Engineering ◽  
Self Assembly ◽  
Three Dimensional ◽  
Dimensional Control ◽  
Hydrogen Bonded

Sulfur as hydrogen-bond acceptor in cocrystals of 2-thio-modified thymine

2018 ◽  
Vol 74 (1) ◽  
pp. 21-30 ◽  
Author(s):  
Wilhelm Maximilian Hützler ◽  
Michael Bolte
Keyword(s):  
Hydrogen Bond ◽  
Hydrogen Bonding ◽  
Crystal Engineering ◽  
Rational Design ◽  
Three Dimensional ◽  
Good Reliability ◽  
Hydrogen Bond Acceptor ◽  
Hydrogen Bonding Interactions ◽  
Hydrogen Bonding Site ◽  
Hydrogen Bonded

Doubly and triply hydrogen-bonded supramolecular synthons are of particular interest for the rational design of crystal and cocrystal structures in crystal engineering since they show a high robustness due to their high stability and good reliability. The compound 5-methyl-2-thiouracil (2-thiothymine) contains an ADA hydrogen-bonding site (A = acceptor and D = donor) if the S atom is considered as an acceptor. We report herein the results of cocrystallization experiments with the coformers 2,4-diaminopyrimidine, 2,4-diamino-6-phenyl-1,3,5-triazine, 6-amino-3H-isocytosine and melamine, which contain complementary DAD hydrogen-bonding sites and, therefore, should be capable of forming a mixed ADA–DAD N—H...S/N—H...N/N—H...O synthon (denoted synthon 3s N·S;N·N;N·O), consisting of three different hydrogen bonds with 5-methyl-2-thiouracil. The experiments yielded one cocrystal and five solvated cocrystals, namely 5-methyl-2-thiouracil–2,4-diaminopyrimidine (1/2), C5H6N2OS·2C4H6N4, (I), 5-methyl-2-thiouracil–2,4-diaminopyrimidine–N,N-dimethylformamide (2/2/1), 2C5H6N2OS·2C4H6N4·C3H7NO, (II), 5-methyl-2-thiouracil–2,4-diamino-6-phenyl-1,3,5-triazine–N,N-dimethylformamide (2/2/1), 2C5H6N2OS·2C9H9N5·C3H7NO, (III), 5-methyl-2-thiouracil–6-amino-3H-isocytosine–N,N-dimethylformamide (2/2/1), (IV), 2C5H6N2OS·2C4H6N4O·C3H7NO, (IV), 5-methyl-2-thiouracil–6-amino-3H-isocytosine–N,N-dimethylacetamide (2/2/1), 2C5H6N2OS·2C4H6N4O·C4H9NO, (V), and 5-methyl-2-thiouracil–melamine (3/2), 3C5H6N2OS·2C3H6N6, (VI). Synthon 3s N·S;N·N;N·O was formed in three structures in which two-dimensional hydrogen-bonded networks are observed, while doubly hydrogen-bonded interactions were formed instead in the remaining three cocrystals whereby three-dimensional networks are preferred. As desired, the S atoms are involved in hydrogen-bonding interactions in all six structures, thus illustrating the ability of sulfur to act as a hydrogen-bond acceptor and, therefore, its value for application in crystal engineering.

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.

Crystal Engineering: Lattice Inclusion Based on O–H···O Hydrogen-Bonded Self-Assembly and Guest-Induced Structural Mimicry

2012 ◽  
Vol 77 (18) ◽  
pp. 7858-7865 ◽  
Author(s):  
Alankriti Bajpai ◽  
Palani Natarajan ◽  
Paloth Venugopalan ◽  
Jarugu Narasimha Moorthy
Keyword(s):  
Crystal Engineering ◽  
Self Assembly ◽  
Hydrogen Bonded

Hydrogen-bonded assemblies in the molecular crystals of 2,2′-thiodiacetic acid with ethylenediamine ando-phenylenediamine

2017 ◽  
Vol 73 (2) ◽  
pp. 97-103 ◽  
Author(s):  
V. Gomathi ◽  
C. Theivarasu
Keyword(s):  
Crystal Engineering ◽  
Mechanical Stability ◽  
Three Dimensional ◽  
Molecular Crystals ◽  
Charge Transfer Complexes ◽  
Supramolecular Network ◽  
One Dimensional ◽  
Supramolecular Networks ◽  
Supramolecular Chains ◽  
Hydrogen Bonded

Carboxylate molecular crystals have been of interest due to the presence of hydrogen bonding, which plays a significant role in chemical and crystal engineering, as well as in supramolecular chemistry. Acid–base adducts possess hydrogen bonds which increase the thermal and mechanical stability of the crystal. 2,2′-Thiodiacetic acid (Tda) is a versatile ligand that has been widely explored, employing its multidendate and chelating coordination abilities with many metals; however, charge-transfer complexes of thiodiacetic acid have not been reported. Two salts, namely ethylenediaminium 2,2′-thiodiacetate, C2H10N22+·C4H4O4S22−, denoted Tdaen, and 2-aminoanilinium 2-(carboxymethylsulfanyl)acetate, C6H9N2+·C4H5O4S−, denoted Tdaophen, were synthesized and characterized by IR,1H and13C NMR spectroscopies, and single-crystal X-ray diffraction. In these salts, Tda reacts with the aliphatic (ethylenediamine) and aromatic (o-phenylenediamine) diamines, and deprotonates them to form anions with different valencies and different supramolecular networks. In Tdaen, the divalent Tda2−anions form one-dimensional linear supramolecular chains and these are extended into a three-dimensional sandwich-type supramolecular network by interaction with the ethylenediaminium cations. However, in Tdaophen, the monovalent Tda−anions form one-dimensional zigzag supramolecular chains, which are extended into a three-dimensional supramolecular network by interaction with the 2-aminoanilinium cations. Thus, both three-dimensional structures display different ring motifs. The structures of these diamines, which are influenced by hydrogen-bonded assemblies in the molecular crystals, are discussed in detail.

scholarly journals Supramolecular Hydrogen Bonded 3D Molecular Self Assembly Constructed from [(Co (nicotinamide)2(thiocyanate)2(H2O)2] Complex Showing Anti-ferromagnetic Character

2014 ◽  
Vol 10 (6) ◽  
pp. 2864-2874
Author(s):  
Deepanjali Pandey ◽  
Shahid S.Narvi ◽  
Siddhartha Chaudhuri
Keyword(s):  
Self Assembly ◽  
Three Dimensional ◽  
Two Dimensional ◽  
X Ray Diffraction ◽  
Spin Orbital ◽  
Space Group ◽  
X Ray ◽  
Susceptibility Data ◽  
Ferromagnetic Character ◽  
Hydrogen Bonded

A new three dimensional hydrogen bonded cobalt frame work from [Co(nicotinamide)2(thiocyanate)2(H2O)2] was synthesized and characterized by X-ray diffraction, magnetism ,TGA and IR spectroscopy. The compound crystallizes in Triclinic space group P-1 with a = 7.5475(19), b = 8.054(2), c =8.932(2). Alpha=73.347(4), beta=70.067(4), gamma=66.559(4) with space group P-1 Z = 1, 'C14 H16 N6 Co O4 S2', Mr =455.38, F(000) = 233 and μ(MoKα) =0.71073 mm-1. The final R = 0.0497 and wR = 0.1461 for 4185 observed reflections with I > 2σ(I) and R = 0.0721 and wR = 0.1619 for all data. X-ray diffraction analyses revealed that Co(1) is linked by the nicotinamide ligands to form the ladder shape along the c axis, which is further extended into two-dimensional networks via the joint of Co(2) along the a axis. Moreover, these two dimensional motifs are interconnected by the thiocyanate S...H bridges to form a complicated 3-D polymeric framework. The magnetic susceptibility data at 1000Oe external field in the temperature range 2-300 K obeys the Curie-Weiss law, giving θ = -24.12 K and C =2.43  thus indicating a dominant strong antiferromagnetic interaction and/or spin orbital coupling between the Co (II) ions. 

scholarly journals ZnII Complexes Based on Hybrid N-Pyrazole, N′-imine Ligands: Synthesis, X-Ray Crystal Structure, NMR Characterisation, and 3D Supramolecular Properties

2015 ◽  
Vol 68 (5) ◽  
pp. 749 ◽  
Author(s):  
Miguel Guerrero ◽  
Lourdes Rivas ◽  
Teresa Calvet ◽  
Mercè Font-Bardia ◽  
Josefina Pons
Keyword(s):  
Crystal Engineering ◽  
Self Assembly ◽  
High Efficiency ◽  
Present Report ◽  
Three Dimensional ◽  
Molecular Complexes ◽  
X Ray ◽  
Elemental Analyses ◽  
Intermolecular Contacts ◽  
Bonding Properties

The present report is on the synthesis of two new 3-imine-3,5-dimethylpyrazole ligands, N-[3-(3,5-dimethyl-1H-pyrazol-1-yl)propylidene]ethylamine (L1) and N-[3-(3,5-dimethyl-1H-pyrazol-1-yl)propylidene]propylamine (L2). These ligands form molecular complexes with the formula [ZnCl2(L)] (L = L1 (1) and L2 (2)) when the reacting with ZnCl2 in a metal (M)/ligand (L) ratio of 1 : 1. These new ZnII complexes have been characterised by elemental analyses, conductivity measurements, mass spectrometry, and infrared, 1H and 13C{1H} NMR spectroscopy techniques. The two crystalline structures of complexes 1 and 2 have been solved by X-ray diffraction methods. Finally, we have studied the self-assembly three-dimensional supramolecular structure through different intra- and intermolecular contacts. The application of these ZnII complexes in supramolecular crystal engineering is interesting due to (1) the easy preparation and the high efficiency of this system and (2) the different bonding properties of the heteroatoms (N-pyrazole vs N-imine) present in the structure of the ligands.

A novel three-dimensional framework constructed by 2-[(1H-imidazol-1-yl)methyl]-1H-benzimidazole and infinite chains of hydrogen-bonded water molecules

2009 ◽  
Vol 65 (3) ◽  
pp. o85-o87 ◽  
Author(s):  
De-Qiang Qi ◽  
Gui-Ge Hou ◽  
Jian-Ping Ma ◽  
Ru-Qi Huang ◽  
Yu-Bin Dong
Keyword(s):  
Self Assembly ◽  
Organic Molecule ◽  
Three Dimensional ◽  
Water Molecules ◽  
Biological Processes ◽  
Stability Function ◽  
Hydrogen Bond Acceptor ◽  
One Dimensional ◽  
Conformation Stability ◽  
Hydrogen Bonded

A novel three-dimensional framework of 2-[(1H-imidazol-1-yl)methyl]-1H-benzimidazole dihydrate, C11H10N4·2H2O orL·2H2O, (I), in whichLacts as both hydrogen-bond acceptor and donor in the supramolecular construction with water, has been obtained by self-assembly reaction ofLwith H2O. The two independent water molecules are hydrogen bonded alternately with each other to form a one-dimensional infinite zigzag water chain. These water chains are linked by the benzimidazole molecules into a three-dimensional framework, in which each organic molecule is hydrogen bonded by three water molecules. This study shows that the diversity of hydrogen-bonded patterns plays a crucial role in the formation of the three-dimensional framework. More significantly, as water molecules are important in contributing to the conformation, stability, function and dynamics of biomacromolecules, the infinite chains of hydrogen-bonded water molecules seen in (I) may be a useful model for water in other chemical and biological processes.

A new three-dimensional manganese(II) coordination polymer based on the 1,3,5-tris[(1H-imidazol-1-yl)methyl]benzene ligand

2016 ◽  
Vol 72 (11) ◽  
pp. 895-900
Author(s):  
Xin-Hua Lu ◽  
Kai-Long Zhong
Keyword(s):  
Coordination Polymer ◽  
Crystal Engineering ◽  
Self Assembly ◽  
Three Dimensional ◽  
Dimensional Structure ◽  
X Ray Diffraction ◽  
Ligand Coordination ◽  
Metal Organic ◽  
And Control ◽  
Methyl Benzene

The self-assembly of coordination polymers and the crystal engineering of metal–organic coordination frameworks have attracted great interest, but it is still a challenge to predict and control the compositions and structures of the complexes. Employing multidentate organic ligands and suitable metal ions to construct inorganic–organic hybrid materials through metal–ligand coordination and hydrogen-bonding interactions has become a major strategy. Recently, imidazole-containing multidentate ligands that contain an aromatic core have received much attention. A new three-dimensional MnIIcoordination polymer based on 1,3,5-tris[(1H-imidazol-1-yl)methyl]benzene, namely poly[(ethane-1,2-diol-κO)(μ-sulfato-κ2O:O′){μ3-1,3,5-tris[(1H-imidazol-1-yl)methyl]benzene-κ3N:N′:N′′}manganese(II)], [Mn(SO4)(C18H18N6)(C2H6O2)]n, was synthesized and characterized by elemental analysis, IR spectroscopy and single-crystal X-ray diffraction. Crystal structural analysis shows that there are two kinds of crystallographically independent MnIIcentres, each lying on a centrosymmetric position and having a similar six-coordinated octahedral structure. One is coordinated by four N atoms from four 1,3,5-tris[(1H-imidazol-1-yl)methyl]benzene (timb) ligands and two O atoms from two different bridging sulfate anions. The second is surrounded by two timb N atoms and four O atoms, two from sulfate anions and two from two ethane-1,2-diol ligands. The tripodal timb ligand bridges neighbouring MnIIcentres to generate a two-dimensional layered structure running parallel to theabplane. Adjacent layers are further bridged by sulfate anions, resulting in a three-dimensional structure with3,4,6-ctopology. Thermogravimetric analysis of the title polymer shows that it is stable up to 533 K. The first weight loss between 533 and 573 K corresponds to the release of coordinated ethane-1,2-diol molecules, and further decomposition occurred at 648 K.

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