scholarly journals Parallel-stacked aromatic molecules in hydrogen-bonded inorganic frameworks

2021 ◽  
Vol 12 (1) ◽  
Author(s):  
Masayasu Igarashi ◽  
Takeshi Nozawa ◽  
Tomohiro Matsumoto ◽  
Fujio Yagihashi ◽  
Takashi Kikuchi ◽  
...  
Keyword(s):  
Hydrogen Bonds ◽  
Building Block ◽  
Materials Science ◽  
Chemical Space ◽  
Three Dimensional ◽  
Inorganic Materials ◽  
Orthosilicic Acid ◽  
Aromatic Molecules ◽  
Pure Benzene ◽  
Hydrogen Bonded

AbstractBy precisely constructing molecules and assembling these into well-defined supramolecular structures, novel physical properties and functionalities can be realized, and new areas of the chemical space can be accessed. In both materials science and biology, a deeper understanding of the properties and exploitation of the reversible character of weak bonds and interactions, such as hydrogen bonds and π–π interactions, is anticipated to lead to the development of materials with novel properties and functionalities. We apply the hydrogen-bonded organic frameworks (HOFs) strategy to inorganic materials science using the cubic octamer of orthosilicic acid, [Si8O12][OH]8, as a building block, and find that various types of hydrogen-bonded inorganic frameworks (HIFs). We succeed in parallel π-stacking pure benzene, thiophene, selenophene, p-benzoquinone, thiophene·p-benzoquinone, and benzene·p-benzoquinone polymers infinitely. These polymers interact via their π-systems by taking advantage of the flexible pores of the three-dimensional nano-honeycomb HIFs, which consist of periodic wide and narrow segments.

scholarly journals Isotypic MnIIand FeIIbinuclear complexes of the ligand 5,6-bis(pyridin-2-yl)-pyrazine-2,3-dicarboxylic acid

2016 ◽  
Vol 72 (10) ◽  
pp. 1412-1416
Author(s):  
Monserrat Alfonso ◽  
Helen Stoeckli-Evans
Keyword(s):  
Hydrogen Bonds ◽  
Dicarboxylic Acid ◽  
Metal Ion ◽  
Three Dimensional ◽  
Water Molecules ◽  
Inversion Symmetry ◽  
Π Interactions ◽  
Metal Atoms ◽  
Hydrogen Bonded

The title isotypic complexes, bis[μ-5,6-bis(pyridin-2-yl)pyrazine-2,3-dicarboxylato]-κ4N1,O2,N6:O3;κ4O3:N1,O2,N6-bis[diaquamanganese(II)] tetrahydrate, [Mn2(C16H8N4O4)2(H2O)4]·4H2O, (I), and bis[μ-5,6-bis(pyridin-2-yl)pyrazine-2,3-dicarboxylato]-κ4N1,O2,N6:O3;κ4O3:N1,O2,N6-bis[diaquairon(II)] tetrahydrate, [Fe2(C16H8N4O4)2(H2O)4]·4H2O, (II), are, respectively, the manganese(II) and iron(II) complexes of the ligand 5,6-bis(pyridin-2-yl)-pyrazine-2,3-dicarboxylic acid. The complete molecule of each complex is generated by inversion symmetry. Each metal ion is coordinated by a pyrazine N atom, a pyridine N atom, two carboxylate O atoms, one of which is bridging, and two water O atoms. The metal atoms haveMN2O4coordination geometries and the complexes have a cage-like structure. In the crystals of both compounds, the complexes are linked by O—H...O and O—H...N hydrogen bonds involving the coordinating water molecules, forming chains along [100]. These chains are linked by O—H...O hydrogen bonds involving the non-coordinating water molecules, forming layers parallel to (011). The layers are linked by pairs of C—H...O hydrogen bonds and offset π–π interactions, so forming a hydrogen-bonded three-dimensional framework.

Reaction-path calculations and crystal structures of 1,1′-(ethylene-1,2-diyl)dipyridinium dichloride dihydrate and 1,1′-(ethylene-1,2-diyl)dipyridinium dibromide

2016 ◽  
Vol 72 (2) ◽  
pp. 112-118
Author(s):  
Mwaffak Rukiah ◽  
Mahmoud M. Al-Ktaifani ◽  
Mohammad K. Sabra
Keyword(s):  
Hydrogen Bonds ◽  
Crystal Engineering ◽  
Materials Science ◽  
Three Dimensional ◽  
X Ray Diffraction ◽  
Substitution Reactions ◽  
Nucleophilic Substitutions ◽  
Triclinic Space Group ◽  
Pyridinium Bromide ◽  
Multinuclear Nmr Spectroscopy

The design of new organic–inorganic hybrid ionic materials is of interest for various applications, particularly in the areas of crystal engineering, supramolecular chemistry and materials science. The monohalogenated intermediates 1-(2-chloroethyl)pyridinium chloride, C5H5NCH2CH2Cl+·Cl−, (I′), and 1-(2-bromoethyl)pyridinium bromide, C5H5NCH2CH2Br+·Br−, (II′), and the ionic disubstituted products 1,1′-(ethylene-1,2-diyl)dipyridinium dichloride dihydrate, C12H14N22+·2Cl−·2H2O, (I), and 1,1′-(ethylene-1,2-diyl)dipyridinium dibromide, C12H14N22+·2Br−, (II), have been isolated as powders from the reactions of pyridine with the appropriate 1,2-dihaloethanes. The monohalogenated intermediates (I′) and (II′) were characterized by multinuclear NMR spectroscopy, while (I) and (II) were structurally characterized using powder X-ray diffraction. Both (I) and (II) crystallize with half the empirical formula in the asymmetric unit in the triclinic space groupP\overline{1}. The organic 1,1′-(ethylene-1,2-diyl)dipyridinium dications, which display approximateC2hsymmetry in both structures, are situated on inversion centres. The components in (I) are linkedviaintermolecular O—H...Cl, C—H...Cl and C—H...O hydrogen bonds into a three-dimensional framework, while for (II), they are connectedviaweak intermolecular C—H...Br hydrogen bonds into one-dimensional chains in the [110] direction. The nucleophilic substitution reactions of 1,2-dichloroethane and 1,2-dibromoethane with pyridine have been investigated byab initioquantum chemical calculations using the 6–31G** basis. In both cases, the reactions occur in two exothermic stages involving consecutive SN2 nucleophilic substitutions. The isolation of the monosubstituted intermediate in each case is strong evidence that the second step is not fast relative to the first.

Hydrogen-Bonded Three-Dimensional Molecular Architectures Featuring Carboxylate - Imidazole - Zinc Triad Systems

2002 ◽  
Vol 55 (11) ◽  
pp. 741 ◽  
Author(s):  
Jin-Hua Yang ◽  
Shao-Liang Zheng ◽  
Jun Tao ◽  
Gao-Feng Liu ◽  
Xiao-Ming Chen
Keyword(s):  
Hydrogen Bonds ◽  
Critical Role ◽  
Three Dimensional ◽  
Water Molecules ◽  
Molecular Architecture ◽  
Lattice Water ◽  
Carboxylate Oxygen ◽  
Polymeric Chains ◽  
Molecular Architectures ◽  
Hydrogen Bonded

Two complexes, [Zn(Him)2(mpa)] (1) and [Zn(Him)2(tpa)]·H2O (2) (Him = imidazole, mpa = m-phthalate, and tpa = terephthalate), have been prepared and structurally characterized, revealing two different three-dimensional hydrogen-bonded molecular architectures. Each features [Zn(Him)2(dicarboxylate)] zigzag polymeric chains and intermolecular N–H…O hydrogen bonds between the uncoordinated Him nitrogen atoms and carboxylate oxygen atoms that are similar to the carboxylate–histidine–zinc triad systems in zinc(II) enzymes. The lattice water molecules in complex (2) play a critical role in the formation of a three-dimensional hydrogen-bonded molecular architecture.

Synthesis and Crystal Structure of [(CH2)6N4CH3]2[CoCl4]

2002 ◽  
Vol 55 (9) ◽  
pp. 561 ◽  
Author(s):  
W. Li ◽  
S.-L. Zheng ◽  
C.-R. Zhu ◽  
Y.-X. Tong ◽  
X.-M. Chen
Keyword(s):  
Crystal Structure ◽  
Nitrogen Atom ◽  
Hydrogen Bonds ◽  
Three Dimensional ◽  
Title Complex ◽  
Chlorine Atoms ◽  
Synthesis And Crystal Structure ◽  
Methylene Groups ◽  
Self Assembled ◽  
Hydrogen Bonded

The interesting three-dimensional hydrogen-bonded self-assembled network of [(CH2)6N4CH3]+ cations and [CoCl4]2– anions has been prepared and structurally characterized. In the title complex, the quaternization of one hexamethylenetetramine nitrogen atom has been trapped, and further stabilized by the large [CoCl4]2– anions, featuring C–H���Cl hydrogen bonds (3.497–3.709 �) between the methylene groups of [(CH2)6N4CH3]+ cations and the chlorine atoms of the [CoCl4]2– anions.

Thymine hydrogen peroxide 0.55-solvate 0.45-hydrate

2007 ◽  
Vol 63 (11) ◽  
pp. o4483-o4483 ◽  
Author(s):  
Andrei V. Churakov ◽  
Judith A. K. Howard
Keyword(s):  
Hydrogen Peroxide ◽  
Hydrogen Bonds ◽  
Three Dimensional ◽  
Water Molecules ◽  
Hydrogen Bonded

Thymine crystallizes from 50% hydrogen peroxide to give the title hydrogen peroxide water solvate, C5H6N2O2·0.55H2O2·0.45H2O. The disordered peroxide and water molecules occupy the same positions. Thymine molecules are linked together by N—H...O hydrogen bonds forming chains parallel to the ac diagonal. Hydrogen peroxide molecules are combined by O—H...O hydrogen bonds to give chains parallel to the c axis. Both kinds of chains are organized in a three-dimensional hydrogen-bonded network.

Associations of squaric acid and its anions as multiform building blocks of hydrogen-bonded molecular crystals

2001 ◽  
Vol 57 (6) ◽  
pp. 859-865 ◽  
Author(s):  
Gastone Gilli ◽  
Valerio Bertolasi ◽  
Paola Gilli ◽  
Valeria Ferretti
Keyword(s):  
Hydrogen Bonds ◽  
Crystal Engineering ◽  
Negative Charge ◽  
Three Dimensional ◽  
Molecular Crystals ◽  
Building Blocks ◽  
Squaric Acid ◽  
Orthosilicic Acid ◽  
Molecular Plane ◽  
Dimensional Crystal

Squaric acid, H2C4O4 (H2SQ), is a completely flat diprotic acid that can crystallize as such, as well as in three different anionic forms, i.e. H2SQ·HSQ−, HSQ− and SQ2−. Its interest for crystal engineering studies arises from three notable factors: (i) its ability of donating and accepting hydrogen bonds strictly confined to the molecular plane; (ii) the remarkable strength of the O—H...O bonds it may form with itself which are either of resonance-assisted (RAHB) or negative-charge-assisted [(−)CAHB] types; (iii) the ease with which it may donate a proton to an aromatic base which, in turn, back-links to the anion by strong low-barrier N—H+...O1/2− charge-assisted hydrogen bonds. Analysis of all the structures so far known shows that, while H2SQ can only crystallize in an extended RAHB-linked planar arrangement and SQ2− tends to behave much as a monomeric dianion, the monoanion HSQ− displays a number of different supramolecular patterns that are classifiable as β-chains, α-chains, α-dimers and α-tetramers. Partial protonation of these motifs leads to H2SQ·HSQ− anions whose supramolecular patterns include ribbons of dimerized β-chains and chains of emiprotonated α-dimers. The topological similarities between the three-dimensional crystal chemistry of orthosilicic acid, H4SiO4, and the two-dimensional one of squaric acid, H2C4O4, are finally stressed.

A hydrogen-bonded tetramer in (2RS,4SR)-7-bromo-2-(2-methylphenyl)-2,3,4,5-tetrahydro-1H-naphtho[1,2-b]azepin-4-ol and a three-dimensional hydrogen-bonded framework in (2RS,4SR)-2-(3-methylthiophen-2-yl)-2,3,4,5-tetrahydro-1H-naphtho[1,2-b]azepin-4-ol

2013 ◽  
Vol 69 (4) ◽  
pp. 448-452 ◽  
Author(s):  
Andrés F. Yépes ◽  
Alirio Palma ◽  
Justo Cobo ◽  
Christopher Glidewell
Keyword(s):  
Hydrogen Bonds ◽  
Three Dimensional ◽  
Space Groups ◽  
Dimensional Array ◽  
Compound Ii ◽  
Related Compounds ◽  
Hydrogen Bonded

(2RS,4SR)-7-Bromo-2-(2-methylphenyl)-2,3,4,5-tetrahydro-1H-naphtho[1,2-b]azepin-4-ol, C21H20BrNO, (I), and (2RS,4SR)-2-(3-methylthiophen-2-yl)-2,3,4,5-tetrahydro-1H-naphtho[1,2-b]azepin-4-ol, C19H19NOS, (II), both crystallize withZ′ = 2 in the space groupsP21/candCc, respectively; compound (II) crystallizes as a nonmerohedral twin, with twin fractions 0.183 (2) and 0.817 (2). The molecules of (I) are linked by O—H...O and O—H...N hydrogen bonds to form a cyclic centrosymmetricR44(16) tetramer. The molecules of (II) are linked by O—H...O hydrogen bonds to form aC22(4) chain and these chains are weakly linked by a single C—H...π(thienyl) interaction to form a three-dimensional array. Comparisons are made with some related compounds.

scholarly journals Topological study of diverse hydrogen-bonded patterns found in a system of a nickel(II) complex and the sulfate anion

2018 ◽  
Vol 74 (3) ◽  
pp. 351-359
Author(s):  
Miguel Angel Harvey ◽  
Sebastián Suarez ◽  
Pavel N. Zolotarev ◽  
Davide M. Proserpio ◽  
Ricardo Baggio
Keyword(s):  
Hydrogen Bonds ◽  
Crystal Structures ◽  
Three Dimensional ◽  
Sulfate Anion ◽  
One Dimensional ◽  
Space Groups ◽  
Striking Resemblance ◽  
The Third ◽  
Reference Framework ◽  
Hydrogen Bonded

A nickel(II) coordination complex, bis[2,6-bis(1H-benzimidazol-2-yl-κN3)pyridine-κN]nickel(II) sulfate, [Ni(C19H13N5)2]SO4or [Ni(H2L)2]SO4, having four peripheral tetrahedrally oriented N—H donor units, combines with sulfate bridges to create hydrogen-bonded structures of varied dimensionality. The three crystal structures reported herein in the space groupsP212121,I\overline{4} andPccnare defined solely by strong charge-assisted N—H...O hydrogen bonds and contain disordered guests (water and dimethylformamide) that vary in size, shape and degree of hydrophilicity. Two of the compounds are channelled solids with three-dimensional structures, while the third is one-dimensional in nature. In spite of their differences, all three present a striking resemblance to the previously reported anhydrous relative [Guoet al.(2011).Chin. J. Inorg. Chem.27, 1517–1520], which is considered as the reference framework from which all three title compounds are derived. The hydrogen-bonded frameworks are described and compared using crystallographic and topological approaches.

scholarly journals Three closely related dibenzazepine carboxylic acids: hydrogen-bonded aggregation in one, two and three dimensions

2014 ◽  
Vol 70 (3) ◽  
pp. 332-337 ◽  
Author(s):  
Carlos M. Sanabría ◽  
Alirio Palma ◽  
Justo Cobo ◽  
Christopher Glidewell
Keyword(s):  
Carboxylic Acid ◽  
Hydrogen Bonds ◽  
Carboxylic Acids ◽  
Three Dimensional ◽  
Three Dimensions ◽  
Framework Structure ◽  
Hydrogen Bonded

In the structure of (6R*,11R*)-5-acetyl-11-ethyl-6,11-dihydro-5H-dibenzo[b,e]azepine-6-carboxylic acid, C19H19NO3, (I), the molecules are linked into sheets by a combination of O—H...O and C—H...O hydrogen bonds; in the structure of the monomethyl analogue (6RS,11SR)-5-acetyl-11-ethyl-2-methyl-6,11-dihydro-5H-dibenzo[b,e]azepine-6-carboxylic acid, C20H21NO3, (II), the molecules are linked into simpleC(7) chains by O—H...O hydrogen bonds; and in the structure of the dimethyl analogue (6RS,11SR)-5-acetyl-11-ethyl-1,3-dimethyl-6,11-dihydro-5H-dibenzo[b,e]azepine-6-carboxylic acid, C21H23NO3, (III), a combination of O—H...O, C—H...O and C—H...π(arene) hydrogen bonds links the molecules into a three-dimensional framework structure. None of these structures exhibits theR22(8) dimer motif characteristic of simple carboxylic acids.

Sign in / Sign up

Export Citation Format

Share Document