scholarly journals Halogenated building blocks for 2D crystal engineering on solid surfaces: lessons from hydrogen bonding

2019 ◽  
Vol 10 (13) ◽  
pp. 3881-3891 ◽  
Author(s):  
Arijit Mukherjee ◽  
Ana Sanz-Matias ◽  
Gangamallaiah Velpula ◽  
Deepali Waghray ◽  
Oleksandr Ivasenko ◽  
...  
Keyword(s):  
Hydrogen Bonding ◽  
Hydrogen Bonds ◽  
Crystal Engineering ◽  
Halogen Bond ◽  
Building Blocks ◽  
Solid Surfaces

We test whether the similarities between halogen and hydrogen bonds could be used to design a surface-confined halogen-bond based 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.

Strategies for Crystal Engineering of Polar Solids

1993 ◽  
Vol 328 ◽  
Author(s):  
Mike Zaworotko ◽  
S. Subramanian ◽  
L. R. Macgillivray
Keyword(s):  
Hydrogen Bonding ◽  
Hydrogen Bonds ◽  
Crystal Engineering ◽  
Organic Cation ◽  
Polar Materials ◽  
Structural Analogues ◽  
Cubane Cluster ◽  
Self Assembled ◽  
Hydrogen Bonded

ABSTRACTCrystal engineering has been invoked to design structural analogues of two prototypal SHG active solids, p-nitroaniline (pNA) and potassium dihydrogenphosphate (KDP). pNA exists as linear polar strands because of head-to-tail hydrogen bonding between adjacent molecules whereas KDP is a self-assembled hydrogen bonded diamondoid network that becomes polar when the hydrogen bonds align. We detail preparation and crystallographic characterization of two classes of multicomponent solid, organic cation hydrogen sulfates and cocrystals of the cubane cluster [M (CO)3(μ3-OH)]4, which structurally mimic pNA and KDP, respectively. Several of the Multi-component solids are polar and they represent a generic approach to designing new polar materials since one component can be changed without altering the basic architecture within the crystal.

N—H...X (X = Cl and Br) hydrogen bonds in three isomorphous 3,5-dichloropyridinium salts

2017 ◽  
Vol 73 (10) ◽  
pp. 803-809 ◽  
Author(s):  
Ai Wang ◽  
Ulli Englert
Keyword(s):  
Hydrogen Bonds ◽  
Small Molecules ◽  
Crystal Engineering ◽  
Electrostatic Interactions ◽  
Halogen Bond ◽  
Halogen Bonds ◽  
Dipole Orientation ◽  
Halide Ligand ◽  
Van Der Waals Radii ◽  
Short Contacts

Specific short contacts are important in crystal engineering. Hydrogen bonds have been particularly successful and together with halogen bonds can be useful for assembling small molecules or ions into crystals. The ionic constituents in the isomorphous 3,5-dichloropyridinium (3,5-diClPy) tetrahalometallates 3,5-dichloropyridinium tetrachloridozincate(II), (C5H4Cl2N)2[ZnCl4] or (3,5-diClPy)2ZnCl4, 3,5-dichloropyridinium tetrabromidozincate(II), (C5H4Cl2N)2[ZnBr4] or (3,5-diClPy)2ZnBr4, and 3,5-dichloropyridinium tetrabromidocobaltate(II), (C5H4Cl2N)2[CoBr4] or (3,5-diClPy)2CoBr4, arrange according to favourable electrostatic interactions. Cations are preferably surrounded by anions and vice versa; rare cation–cation contacts are associated with an antiparallel dipole orientation. N—H...X (X = Cl and Br) hydrogen bonds and X...X halogen bonds compete as closest contacts between neighbouring residues. The former dominate in the title compounds; the four symmetrically independent pyridinium N—H groups in each compound act as donors in charge-assisted hydrogen bonds, with halogen ligands and the tetrahedral metallate anions as acceptors. The M—X coordinative bonds in the latter are significantly longer if the halide ligand is engaged in a classical X...H—N hydrogen bond. In all three solids, triangular halogen-bond interactions are observed. They might contribute to the stabilization of the structures, but even the shortest interhalogen contacts are only slightly shorter than the sum of the van der Waals radii.

scholarly journals Hydrogen-bonding network in the organic salts of 4-nitrobenzoic acid

2006 ◽  
Vol 4 (3) ◽  
pp. 458-475 ◽  
Author(s):  
Yurii Chumakov ◽  
Yurii Simonov ◽  
Mata Grozav ◽  
Manuela Crisan ◽  
Gabriele Bocelli ◽  
...  
Keyword(s):  
Hydrogen Bonding ◽  
Hydrogen Bonds ◽  
Crystal Structures ◽  
Crystal Packing ◽  
Building Blocks ◽  
Supramolecular Architecture ◽  
Two Dimensional ◽  
Organic Salts ◽  
Nitrobenzoic Acid ◽  
Ionic Forms

AbstractThe crystal structures of six novel salts of 4-nitrobenzoic acid — namely, 2-hydroxyethylammonium 4-nitrobenzoate (I), 2-hydroxypropylammonium 4-nitrobenzoate (II), 1-(hydroxymethyl)propylammonium 4-nitrobenzoate (III), 3-hydroxypropylammonium 4-nitrobenzoate (IV), bis-(2-hydroxyethylammonium) 4-nitrobenzoate (V), morpholinium 4-nitrobenzoate (VI) — containing the same anion but different cations have been studied. The ionic forms of I-VI serve as building blocks of the supramolecular architecture, and in crystals they are held together via ionic N-H···O and O-H···O hydrogen bonds. In the crystal packing the building blocks of I-III are self-assembled via N-H...O, O-H···O and C-H...O hydrogen bonds to form the chains which are further consolidated into two-dimensional layers by the same type of interactions. In IV-VI the chain-like structures have been generated by building blocks.

Crystal Engineering of a New Layered Polyiodide Using 1,9-Diammoniononane as a Flexible Template Cation

2004 ◽  
Vol 59 (10) ◽  
pp. 1114-1117 ◽  
Author(s):  
Guido J. Reiß ◽  
Judith S. Engel
Keyword(s):  
Thermal Analysis ◽  
Hydrogen Bonding ◽  
Raman Spectrum ◽  
Solid State ◽  
Hydrogen Bonds ◽  
Crystal Engineering ◽  
Title Compound ◽  
State Structure ◽  
Cooperative Phenomenon ◽  
Weak Hydrogen Bonds

AbstractThe reaction of 1,9-diaminononane with hydroiodic acid in the presence of iodine gave a compound best described as 1,9-diammoniononane bis-triiodide iodine, (H3N-(CH2)9-NH3)[I3]2 · I2. The structure is built from two crystallographically independent I3− anions, which are connected via secondary I···I interactions to the iodine molecules, and the 1,9-diammonioalkane cations are connected via weak hydrogen bonds to neighbouring iodine atoms. By a cooperative phenomenon, the shape and the functionality of the cation lead to a solid state structure that includes a polyiodide substructure with the formula 2∞[I8]2− or 2∞[I3 · I2 · I3]2−, is best described as a brick-shaped layered array. Its rectangular pores fit excellently with the hydrogen bonding functionality as well as with the conformational needs of the 1,9-diammoniononane template. The Raman spectrum shows typical bands of coordinated triiodide anions and iodine molecules. The thermal analysis (DSC/TG) of the title compound indicates decomposition at temperatures above 210°C.

Hydrogen-Bonded Networks Featuring Yttrium(III) Complexes of N,N’-Dimethylurea (DMU): Preparation and Characterization of [Y(DMU)6][YCl6] and [Y(NO3)3(DMU)3]

2005 ◽  
Vol 60 (4) ◽  
pp. 363-372 ◽  
Author(s):  
Athanassios K. Boudalis ◽  
Vassilios Nastopoulos ◽  
Catherine P. Raptopoulou ◽  
Aris Terzis ◽  
Spyros P. Perlepes
Keyword(s):  
Hydrogen Bonding ◽  
Hydrogen Bonds ◽  
Single Crystal ◽  
Crystal Engineering ◽  
Coordination Complexes ◽  
3D Network ◽  
3D Architecture ◽  
Intramolecular Hydrogen ◽  
Hydrogen Bonded

In order to examine the possibility of using yttrium(III) in the crystal engineering of hydrogenbonded coordination complexes and to compare the molecular and supramolecular YIII/Cl3 or NO3-/DMU chemistry with the already well-developed LnIII/Cl− or NO3−/DMU chemistry (LnIII = lanthanide, DMU = N,N’-dimethylurea), compounds [Y(DMU)6][YCl6] (1) and [Y(NO3)3(DMU)3] (2) have been prepared. The structures of both compounds have been determined by single-crystal Xray diffraction. The structure of 1 consists of octahedral [Y(DMU)6]3+ and [YCl6]3− ions. The YIII ion in 2 is nine-coordinate and ligation is provided by three O-bonded DMU ligands and three bidentate chelating nitrato groups; the coordination polyhedron about the metal can be viewed as a distorted, monocapped square antiprism. The [Y(DMU)6]3+ cations and [YCl6]3− anions self-assemble to form a hydrogen-bonded 3D architecture in 1. Most of the hydrogen-bonding functionalities on the components of 2 create also a 3D network. Two motifs of interionic/intramolecular hydrogen-bonds have been observed: N-H···Cl in 1 and N-H···O(NO3−) in 2. The IR data are discussed in terms of the nature of bonding and the structures of the two complexes

Hydrogen bonding at C=Se acceptors in selenoureas, selenoamides and selones

2016 ◽  
Vol 72 (3) ◽  
pp. 317-325 ◽  
Author(s):  
Dikima Bibelayi ◽  
Albert S. Lundemba ◽  
Frank H. Allen ◽  
Peter T. A. Galek ◽  
Juliette Pradon ◽  
...  
Keyword(s):  
Hydrogen Bond ◽  
Hydrogen Bonding ◽  
Hydrogen Bonds ◽  
Ab Initio ◽  
Crystal Engineering ◽  
Cambridge Structural Database ◽  
Bond Lengths ◽  
Partial Charges ◽  
Structural Database

In recent years there has been considerable interest in chalcogen and hydrogen bonding involving Se atoms, but a general understanding of their nature and behaviour has yet to emerge. In the present work, the hydrogen-bonding ability and nature of Se atoms in selenourea derivatives, selenoamides and selones has been explored using analysis of the Cambridge Structural Database andab initiocalculations. In the CSD there are 70 C=Se structures forming hydrogen bonds, all of them selenourea derivatives or selenoamides. Analysis of intramolecular geometries andab initiopartial charges show that this bonding stems from resonance-induced Cδ+=Seδ−dipoles, much like hydrogen bonding to C=S acceptors. C=Se acceptors are in many respects similar to C=S acceptors, with similar vdW-normalized hydrogen-bond lengths and calculated interaction strengths. The similarity between the C=S and C=Se acceptors for hydrogen bonding should inform and guide the use of C=Se in crystal engineering.

scholarly journals Crystal structures of 2-[3,5-bis(bromomethyl)-2,4,6-triethylbenzyl]isoindoline-1,3-dione and 2-{5-(bromomethyl)-3-[(1,3-dioxoisoindolin-2-yl)methyl]-2,4,6-triethylbenzyl}isoindoline-1,3-dione

2021 ◽  
Vol 77 (9) ◽  
Author(s):  
Manuel Stapf ◽  
Betty Leibiger ◽  
Anke Schwarzer ◽  
Monika Mazik
Keyword(s):  
Crystal Structure ◽  
Hydrogen Bonding ◽  
Hydrogen Bonds ◽  
Crystal Structures ◽  
Molecular Conformation ◽  
Halogen Bond ◽  
Asymmetric Unit ◽  
Space Group ◽  
Π Interactions ◽  
Hydrogen Bonding Interactions

The title compounds, C23H25Br2NO2 (1) and C31H29BrN2O4 (2), crystallize in the space group P21/n with two (1-A and 1-B) and one molecules, respectively, in the asymmetric unit of the cell. The molecular conformation of these compounds is stabilized by intramolecular C—H...O hydrogen bonds and C—H...N or C—H...π interactions. The crystal structure of 1 features a relatively strong Br...O=C halogen bond, which is not observed in the case of 2. Both crystal structures are characterized by the presence of C—H...Br hydrogen bonds and numerous intermolecular C—H...O hydrogen-bonding interactions.

scholarly journals Exploring the Halogen-Bonded Cocrystallization Potential of a Metal-Organic Unit Derived from Copper(ii) Chloride and 4-Aminoacetophenone

Materials ◽  
2020 ◽  
Vol 13 (10) ◽  
pp. 2385
Author(s):  
Vinko Nemec ◽  
Katarina Lisac ◽  
Marin Liović ◽  
Ivana Brekalo ◽  
Dominik Cinčić
Keyword(s):  
Hydrogen Bonding ◽  
Halogen Bond ◽  
Halogen Bonding ◽  
Building Blocks ◽  
Supramolecular Interactions ◽  
X Ray Diffraction ◽  
Square Planar ◽  
Metal Organic ◽  
Acetyl Group ◽  
Conventional Solution

In this work, we describe a novel halogen-bonded metal-organic cocrystal involving a square-planar Cu(ii) complex and 1,4-diiodotetrafluorobenzene (14tfib) by utilizing an amine ligand whose pendant acetyl group enables halogen bonding. The cocrystal was prepared by both mechanochemical synthesis (liquid-assisted grinding) and the conventional solution-based method. Crystal structure determination by single crystal X-ray diffraction revealed that the dominant supramolecular interactions are the I···O halogen bond between 14tfib and CuCl2(aap)2 building blocks, and the N–H···Cl hydrogen bonds between CuCl2(aap)2 molecules. The combination of halogen and hydrogen bonding leads to the formation of a 2D network. Overall, this work showcases an example of the possibility for extending the complexity of metal-organic crystal structures by using halogen bonding in a way that does not affect other hydrogen bonding synthons.

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