Crystal Engineering Using Bis- and Tris-phenols. Adducts with 1,4,8,11-Tetraazacyclotetradecane (Cyclam): Isolated Ladders in the Adduct with 4,4'-Thiodiphenol, Tethered Ladders in the Adduct with 4,4'-Sulfonyldiphenol and Two Interwoven Three-Dimensional Networks in the Adduct with 1,1,1-Tris(4-... (original) (raw)
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Crystal Engineering: Some Further Strategies
Crystal Engineering, 1998
Structural studies currently underway in our group are reported in this paper. Molecular symmetry is rarely carried over into the crystal, posing problems when high-symmetry networks are desired. This is illustrated by the lowsymmetry structure of 2,4,6-trinitromesitylene. However, the involvement of the Cl 3 supramolecular synthon ensures a hexagonal network structure for 2,4,6-tris-(4-chlorophenoxy)-1,3,5-triazine. Arguments following from the equivalence between molecular and supramolecular synthons lead to the tetragonal network structure of the 1:1 complex of tetraphenylmethane and CCl 4 . With a similar reasoning, 4-(triphenylmethyl)benzoic acid is identified as a precursor of a supramolecular wheel-and-axle host substance. The study of novel and weaker intermolecular interactions is often useful. In N,NЈdibenzyl-1,4-cubanedicarboxamide, the acidity of the cubyl C-H groups leads to the formation of C-H⅐⅐⅐O hydrogen bonds. Polymorphism is a difficult challenge for the crystal engineer and, in its most intriguing manifestation, two crystalline forms of a substance appear in the same crystallization batch. This is observed for 4,4-diphenyl cyclohexadienone. The ultimate frontier in the subject is an understanding of the phenomenon of crystallization, and the unexpected crystal structure of quinoxaline, with five symmetry-independent molecules, could possibly represent a case of arrested crystallization. © 1998
Crystal Growth & Design, 2006
The interplay of strong and weak hydrogen bonds has been used to produce self-assembled architectures by the complexation of pentaphenol 1 with the diaza compounds such as pyrazine (pyz), 4,4′-bipyridine (bpy), trans-1,2-bis(4-pyridyl)ethylene (bpy-ethe), and 1,2-bis(4-pyridyl)ethane (bpy-etha). In all cases, the primary recognition patterns involve O-H‚‚‚N and O-H‚‚‚O hydrogen bonds. The crystal structure of complex 1‚pyz involves ladder structures stabilized by π‚‚‚π stacking between the benzene rings of 1 and pyz. Interpenetrating ladder architectures were observed in the crystal lattice of complex 1‚bpy. A network of cyclic cavities and ladder structures dominated the solid lattice of complexes 1‚bpy-ethe and 1‚bpy-etha. Both complexes are isomorphous; they crystallize as dihydrates and also have the same space group, P1 h. In the complex 1‚bpy-ethe, the existence of C-H‚‚‚π interactions involving the double bond of the ethene moiety provides additional stabilization to the three-dimensional (3D) network structure. The formation of various supramolecular motifs from the complexes can be attributed to the 3D structure of molecule 1 and the flexibility of the linking aza molecules in the crystal lattice.
Crystal Engineering and Molecular Architecture
DOAJ (DOAJ: Directory of Open Access Journals), 2007
The aim of this paper is to provide a link between research projects and education to optimize teaching and learning of related subjects. In a research project, three compounds including an intermolecular proton transfer compound, a hydrated carboxylic acid, and a metallic complex were synthesized, all of them have non-covalent interactions such as O−H•••O, O−H•••N and C−H•••O hydrogen bonds as well as van der Waals forces and π-π stacking resulting to different supramolecular structures. The structures of compounds are characterized by single crystal X-ray diffraction method. The classic concepts and definitions related to the subject are given in the last section.
Acta Crystallographica Section E Crystallographic Communications, 2015
The structure of the 1:2 co-crystalline adduct C8H16N4·2C6H5BrO, (I), from the solid-state reaction of 1,3,6,8-tetraazatricyclo[4.4.1.13,8]dodecane (TATD) and 4-bromophenol, has been determined. The asymmetric unit of the title co-crystalline adduct comprises a half molecule of aminal cage polyamine plus a 4-bromophenol molecule. A twofold rotation axis generates the other half of the adduct. The primary inter-species association in the title compound is through two intermolecular O—H...N hydrogen bonds. In the crystal, the adducts are linked by weak non-conventional C—H...O and C—H...Br hydrogen bonds, giving a two-dimensional supramolecular structure parallel to thebcplane.
Acta Crystallographica Section E Crystallographic Communications, 2015
In the title ternary co-crystalline adduct, C7H14N4·2C6H5NO3, molecules are linked by two intermolecular O—H...N hydrogen bonds, forming a tricomponent aggregates in the asymmetric unit. The hydrogen-bond formation to one of the N atoms is enough to induce structural stereoelectronic effects in the normal donor→acceptor direction. In the title adduct, the two independent nitrophenol molecules are essentially planar, with maximum deviations of 0.0157 (13) and 0.0039 (13) Å. The dihedral angles between the planes of the nitro group and the attached benzene rings are 4.04 (17) and 5.79 (17)°. In the crystal, aggregates are connected by C—H...O hydrogen bonds, forming a supramolecular dimer enclosing anR66(32) ring motif. Additional C—H...O intermolecular hydrogen-bonding interactions form a second supramolecular inversion dimer with anR22(10) motif. These units are linkedviaC—H...O and C—H...N hydrogen bonds, forming a three-dimensional network.
Crystal Engineering: A Brief for the Beginners
Acta Scientific Pharmaceutical Sciences, 2021
Crystals are formed by aggregation of molecules in solution. This phenomenon encourages several questions. Among them few are, how do these aggregations happen to form crystals? Why do same molecules adopt more than one crystal structure? Why does solvent occupy some crystal structures? How does crystal structure can be designed with a specified coordination of molecules and/ or ions with a specified property? What are the relationships between crystal structures and properties, for molecular crystals? At present several queries are being resolved by the crystal engineering community; a larger community constructed by organic, inorganic and physical chemists, crystallographers and solid-state scientists. This article provides brief idea to provide a basic introduction to crystal engineering and this fascinating and important subject that has moved from the fringes into the mainstream of chemistry.
Angewandte Chemie International Edition, 2011
During the past decade porous metal-organic material (MOM) networks constructed from metal-based nodes (metal ions or metal clusters) and bridging organic ligand (linkers) have attracted ever increasing scientific interest. [1] Their modular nature imparts structural and compositional diversity, tunable functionality, and multiple properties within a single material. In particular, that MOMs can exhibit extralarge surface area means that they represent a uniquely promising class of materials to solve technological challenges related to gas storage and separation, environmental remediation, catalysis, sensing, and drug delivery. Crystal engineering played a major role in the early development of MOMs as exemplified by the high symmetry nets that can be generated by linking polygonal or polyhedral nodes such as tetrahedra (dia), octahedra (pcu), [3c] squares (nbo), [3c, 4] and trigonal prisms (acs). The aforementioned nets might be described as platforms because they are fine-tunable in terms of both scale and properties as there are many nodes and linkers that can sustain these structures. Pyridyl linkers such as 4,4'-bipyridine were initially exploited in such a capacity [6] but the majority of extra-large surface area MOMs are based upon carboxylate linkers such as benzene-1,3-dicarboxylic acid (1,3-BDC), [7] benzene-1,4-dicarboxylic acid (1,4-BDC), [8] and benzene-1,3,5-tricarboxylic acid (BTC). Such linkers complement synthetically accessible and highly symmetrical metal carboxylate nodes such as [Cu 2 (CO 2 ) 4 ], [Zn 4 (m 4 -O)-(CO 2 ) 6 ] and [{M 3 (m 3 -O)(CO 2 )} 6 ] (M = Cr, Fe). The exploitation of [Cu 2 (CO 2 ) 4 ], the "square paddlewheel", has proven to be particularly fruitful since ligand design or the use of mixed ligands facilitates a plethora of highly porous polyhedral nets. [{M 3 (m 3 -O)(CO 2 )} 6 ], the "trigonal prism", has also afforded highly porous materials, as exemplified by MIL-100 and MIL-101. However, even though this node is remarkably robust, [14] its structures tend to form only microcrystalline materials and require harsh synthetic conditions. We describe herein a crystal engineering strategy that exploits preformed molecular building blocks (MBBs) based upon water-stable trigonal prisms that are decorated with pyridyl moieties. A two-step modular approach that opens up a broad new class of bimetallic MOMs is thereby facilitated. Two-step processes to form heterobimetallic frameworks are known and are based on the synthesis of a metal complex that is subsequently connected to a different metal ion. To the best of our knowledge, high-connectivity metal complexes that afford high symmetry nets with extra-large channels have not yet been studied in this context. Our twostep process involves isolation of a trigonal prism decorated by pyridyl moieties and then coordinating this highly soluble trigonal-prismatic Primary Molecular Building Block (tp-PMBB-1) to different metals through its six exodentate pyridyl moieties (Scheme 1). We coin the term PMMB to draw analogies to the primary building unit (PBU) in zeolite chemistry. In this context the different connections of PMBBs to various Secondary Molecular Building Blocks (SMBBs) lead to the structural diversity. This approach enables us to exploit both metal-carboxylate and metal-pyridyl bonds and ensures that the nets thereby generated will be positively charged. The first three examples of such nets, tp-PMBB-1snx-1, -snw-1, and -stp-1 (nomenclature describes both the primary building block and the topology of the resulting net) are described herein.
Zeitschrift für Kristallographie - New Crystal Structures
C22H42N6, triclinic, P 1 ‾ overline1\overline{1}overline1 (no. 2), a = 8.3115(2) Å, b = 8.8263(2) Å, c = 9.7688(2) Å, α = 111.490 ( 2 ) ° 111.490(2)circ111.490(2){}^{\circ}111.490(2)circ , β = 115.056 ( 2 ) ° 115.056(2)circ115.056(2){}^{\circ}115.056(2)circ , γ = 93.681 ( 2 ) ° 93.681(2)circ93.681(2){}^{\circ}93.681(2)circ , V = 583.25(3) Å3, Z = 1, R gt (F) = 0.0465, wR ref (F 2) = 0.1351, T = 294 K.
Acta Crystallographica Section E: Crystallographic Communications, 2017
The asymmetric unit of the title co-crystalline adduct, 1,3,6,8-tetraazatricyclo-[4.4.1.1 3,8 ]dodecane (TATD)-4-iodophenol (1/2), C 8 H 16 N 4 Á2C 6 H 5 IO, comprises a half molecule of the aminal cage polyamine plus a 4-iodophenol molecule. A twofold rotation axis generates the other half of the adduct. The components are linked by two intermolecular O-HÁ Á ÁN hydrogen bonds. The adducts are further linked into a three-dimensional framework structure by a combination of NÁ Á ÁI halogen bonds and weak non-conventional C-HÁ Á ÁO and C-HÁ Á ÁI hydrogen bonds. research communications Acta Cryst. (2017). E73, 1692-1695 Rivera et al. C 8 H 16 N 4 Á2C 6 H 5 IO 1695 supporting information sup-1
Recent Developments in Crystal Engineering
Crystal Growth & Design, 2011
Crystal Growth & Design PERSPECTIVE increase via weak noncovalent interactions such as hydrogen bonds, and (c) 1D f 3D and 2D f 3D dimensional increase via interpenetration or catenation. 5 Recently, the first China-India-Singapore Symposium on Crystal Engineering held at the National University of Singapore provided an excellent forum and opportunities for the researchers from these three countries to showcase their research and exchange ideas. The focus of this perspective is to review the invited talks which were presented at this symposium by the top researchers from these countries working in the field of crystal engineering, crystal growth, and supramolecular chemistry. A wide range of topics was discussed that includes new directions in organic crystal engineering, fundamental theoretical aspects of supramolecular interactions, crystallization of biomaterials, polymorphism, co-crystals, design of organic crystals, covalent organic frameworks, porous organic frameworks, oxo clusters, rotaxanes, coordination polymers, supramolecular gels, solid-state dynamics and structural transformations, mechanical properties of pharmaceutics, sorption, optical and magnetic properties to applications in graphene and plastic solar cells.