Zirconocene complexes bearing novel 3-dimethylamino-1,2-dihydropentalene derived ligand systems.
Coupling of the N,N-dimethylacrylamides 6a-c with cyclopentadienide resulted in the formation of the substituted 3-dimethylamino-1,2-dihydropentalnenes 2a-c. Deprotonation followed by metallation with CpZrCl(3)·DME gave the substituted zirconocenes 12a-c. The reaction of 3-dimethylamino-1-methyl-dihydropentalene 2a with ZrCl(2)(NMe(2))(2)·2THF resulted in a unique coupling between a pair of the aminodihydropentalene derivatives to yield an unsymmetrically bridged novel ansa-zirconocene framework (9a). Treatment of the 1,1-dimethyl-substituted substrate 2b with this Zr-amido reagent in contrast resulted in a clean deprotonation and formation of the unbridged bis(dimethylaminohydropentalenyl)…
Effect of a Rigid Sulfonamide Bond on Molecular Folding: A Case Study
A disulfonamide compound with bulky aromatic side chains was prepared, and its properties as a potential building block for foldamers were evaluated. Two different solvate crystal forms of the compound were identified and compared to the structures of an analogous oligoamide and related disulfonamides. The disulfonamide is unfolded in one of the solvates, whereas in the other one, a loosely folded conformer stabilized by an intramolecular hydrogen bond is found. Density functional calculations indicated that the loosely folded conformer is slightly more stable than its unfolded isomer. The calculations also identified a third, more tightly folded and more extensively hydrogen bonded, confor…
Structural analysis of two foldamer-type oligoamides – the effect of hydrogen bonding on solvate formation, crystal structures and molecular conformation
Author's Final draft The crystal structures and molecular conformations of two foldamer-type oligoamides were analyzed. One polymorphic form and seven solvates were found for N¹,N³-bis(2-benzamidophenyl)benzene-1,3-dicarboxamide (the benzene variant), and two polymorphic forms and six solvates for N²,N⁶-bis(2-benzamidophenyl)pyridine-2,6-dicarboxamide (the pyridine variant). Three crystal structures of the benzene variant and seven structures of the pyridine variant were solved using single crystal X-ray diffraction. The crystal structures showed that the different modes of intramolecular hydrogen bonding strongly affect the conformation and folding of the molecules, which is most evidently…
Comparison of the polymorphs and solvates of two analogous fungicides—a case study of the applicability of a supramolecular synthon approach in crystal engineering
The polymorphism and solvate formation of thiophanate-ethyl (TE), a fungicidal active, were investigated by solvent crystallization and compared to a close analogue, thiophanate-methyl (TM). Four polymorphs and seven solvates of TE were found and structurally compared with the previously found two polymorphs and fourteen solvates of TM by analyzing the hydrogen bonding patterns and using fingerprint plots, packing coefficients and lattice energies. TE and TM have the same functional groups that can build identical supramolecular synthons. Despite the strong similarities, the polymorphs and solvates of the two actives show significant differences in hydrogen bonding and packing. The results …
Conformational properties and folding analysis of a series of seven oligoamide foldamers
33 crystal structures (11 unsolvated and 22 solvates) of a series of seven oligoamide foldamers were analysed. The crystal structures revealed that despite the structural and environmental differences the series of foldamers prefer only two general conformations, a protohelical @-conformation and a sigmoidal S-conformation. Both conformations also have preferred crystal packing motifs and solvate forming tendencies. Hydrogen bonding was found to be the most decisive factor in conformational preference, but steric properties, the type of the peripheral substituents, as well as solvent and aromatic interactions were also found to have an effect on the conformational details and crystal form. …
Resorcinarene Bis-Thiacrowns: Prospective Host Molecules for Silver Encapsulation
Mixed-donor atom tetramethoxy resorcinarene bis-thiacrown hosts, in which the crown unit contains both hard oxygen and soft sulfur donor atoms, were synthesized for soft metal cation binding. The binding properties were investigated both in solution and in the solid state by NMR spectroscopy and X-ray crystallography. It was found that the resorcinarene bis-thiacrowns were able to complex silver cations with remarkable affinity forming readily 1:2 host–guest complexes in solution. The solid state structures also revealed that the bis-thiacrowns form silver complexes in an unanticipated endo- and exo-cavity fashion within the same host molecule. Both the solution and solid state studies indi…
Solvent driven formation of silver embedded resorcinarene nanorods
Silver complexes of resorcinarene bis-crown-5 were observed to arrange into nanorods of 2.4 nm in diameter. The left- and right-handed isomers of the inherently chiral resorcinarene host are separated into their own entity in the self-assembly process with the periphery of the nanorods consisting of silver cations included in the cavity.
Synthesis and Characterization of theO-Alkylation Products of Resorcinarene
O-Substitution reactions of tetramethoxyresorcinarene with alkyl halides produced a variety of partially O-alkylated resorcinarene derivatives with terminal alkyne functionality. The degree of alkylation was affected by the reactivity of the alkylating halide used. NMR spectroscopy proved to be an ideal tool for analyzing the complex reaction mixtures and the isolated products based on the symmetry and degree of alkylation of the resorcinarene derivatives. Single-crystal X-ray diffraction studies furthermore showed diversity in the self-assembly of the various O-alkylation products that was greatly affected by the degree of alkylation, as well as the nature of the alkyne moiety.
Supramolecular chirality and symmetry breaking of fluoride complexes of achiral foldamers
Aromatic oligoamide foldamers containing a central pyridine-2,6-dicarbonyl motif are partially preorganized to favor the binding of fluoride anions. In the solid state, the foldamer-fluoride complexes form achiral, polar and chiral crystal structures depending on the chemical structure of the foldamer. One of the six foldamers studied here, a C2v symmetrical foldamer (1), formed repeatedly chiral crystal structures when crystallized with tetra-butylammonium fluoride, showing supramolecular bulk chirality and symmetry breaking in crystallization.
Polymorphism and versatile solvate formation of thiophanate-methyl
The polymorphism of a fungicide, thiophanate-methyl (TM), was investigated with conventional solvent screening methods. Two polymorphs, the thermodynamically most stable form I and the less stable form II, were found. TM was also found to crystallize as a plethora of different solvates which produced mostly form II upon desolvation. The structures of form I and form II and the fourteen discovered solvates were solved by single crystal X-ray diffraction. The most stable forms were further characterized by powder diffraction, thermoanalytical (TG/DTA, DSC and thermomicroscopy) and spectroscopic (IR, Raman, ¹³C CP/MAS NMR) methods. peerReviewed
Conformational polymorphism and amphiphilic properties of resorcinarene octapodands
o-Nitroaniline functionalized resorcinarene octapodands 1-5 with pendant methyl, ethyl, pentyl, nonyl or 1-decenyl groups, respectively, were synthesized and their structural properties investigated using X-ray crystallography and NMR spectroscopy. The upper rim of each podand is identical containing flexible side arms, in which rotation around the -OCH(2)CH(2)N- linkers create excellent possibilities for polymorphism. Two conformational polymorphs of acetone solvate of 2 were identified containing different side arm orientation and crystal packing. Compound 1 crystallized from acetone and nitromethane yielding two pseudopolymorphs with different packing motifs. The longer alkyl chains of 3…
Co-crystals of an agrochemical active – A pyridine-amine synthon for a thioamide group
Five novel co-crystals of thiophanate-ethyl (TE), an agrochemical active, with di(2-pyridyl)ketone (1), 2-benzoylpyridine (2), 3-benzoylpyridine (3), 4-phenylpyridine (4) and biphenyl (5) were found and crystal structures of four of them (TE1–TE3, TE5) solved by single crystal X-ray diffraction. Three of the co-crystals (TE1–TE3) form by way of a reliable pyridine-amine hydrogen bond synthon and one (TE5) because of close packing effects. The fifth co-crystal was identified by X-ray powder diffraction. The work demonstrates the usage of a reliable supramolecular synthon for crystal engineering, while concurrently reminds that the close packing of even very similar molecules cannot be fully …
Cyclizations via Frustrated Lewis Pairs: Lewis Acid Induced Intramolecular Additions of Amines to Olefins and Alkynes
Packing incentives and a reliable N–H⋯N–pyridine synthon in co-crystallization of bipyridines with two agrochemical actives
The co-crystallization of agrochemical actives thiophanate-methyl and thiophanate-ethyl with 2,2′-bipyridine, 4,4′-bipyridine and 1,2-bis(4-pyridyl)ethane was investigated with conventional crystallization, the slurry method and liquid-assisted grinding. Co-crystals of both thiophanates with all bipyridines were found and the structures solved with single crystal X-ray diffraction. Whereas the 2,2′-bipyridine co-crystals seem to form because of a combination of weak interactions, and in the case of the thiophanate-methyl, partly because of close packing incentives, the 4,4′-bipyridine and 1,2-bis(4-pyridyl)ethane co-crystals form mainly because of a favourable N–H···N–pyridine hydrogen bond…
Folding Patterns in a Family of Oligoamide Foldamers
A series of small, unsymmetrical pyridine-2,6-dicarboxylamide oligoamide foldamers with varying lengths and substituents at the end groups were synthetized to study their conformational properties and folding patterns. The @-type folding pattern resembled the oxyanion-hole motifs of enzymes, but several alternative folding patterns could also be characterized. Computational studies revealed several alternative conformers of nearly equal stability. These folding patterns differed from each other in their intramolecular hydrogen-bonding patterns and aryl-aryl interactions. In the solid state, the foldamers adopted either the globular @-type fold or the more extended S-type conformers, which w…
Non-Centrosymmetric Tetrameric Assemblies of Tetramethylammonium Halides with Uranyl Salophen Complexes in the Solid State
Ditopic salophen-UO(2) receptors 1-4 and 7 co-crystallize with tetramethylammonium (TMA) chloride and fluoride salts producing good quality crystals amenable for X-ray diffraction characterization. The arrangement of the receptor and salt units in the crystal lattice is such that tetrameric ball-shaped assemblies are formed, where an inner cluster of four TMA cations are surrounded by an outer shell of four UO(2)-bound anions. These elaborate architectures, which occur in all cases, regardless of a certain degree of structural modification on the receptors, lead to lattices that belong to non-centrosymmetric (NCS) space groups. Interestingly, the tetragonal symmetry of the tetrameric ball-s…
Crystalline forms of selected agrochemical actives : design and synthesis of cocrystals
The research described in this disseration covers the crystal form screening of two analogous agrochemical actives, thiophanate-methyl and thiophanate-ethyl, as well as the discovery of seven 4-hydroxybenzoic acid cocrystals of selected agrochemical actives. Polymorphs are crystal forms of a compound that have the same composition, but a different arrangement of molecules. Cocrystals are molecular crystals composed of two or more compounds, and refer mainly to crystals which contain compounds that are solids at standard conditions. Solvates are forms that have molecules of solvent in the crystal lattice and these include hydrates, in which the solvent is water. The crystal forms of organic …
CCDC 1436660: Experimental Crystal Structure Determination
Related Article: Aku Suhonen, Minna Kortelainen, Elisa Nauha, Sanna Yliniemelä-Sipari, Petri M. Pihko, Maija Nissinen|2016|CrystEngComm|18|2005|doi:10.1039/C5CE02458G
CCDC 1436663: Experimental Crystal Structure Determination
Related Article: Aku Suhonen, Minna Kortelainen, Elisa Nauha, Sanna Yliniemelä-Sipari, Petri M. Pihko, Maija Nissinen|2016|CrystEngComm|18|2005|doi:10.1039/C5CE02458G
CCDC 1438546: Experimental Crystal Structure Determination
Related Article: Aku Suhonen, Minna Kortelainen, Elisa Nauha, Sanna Yliniemelä-Sipari, Petri M. Pihko, Maija Nissinen|2016|CrystEngComm|18|2005|doi:10.1039/C5CE02458G
CCDC 1038219: Experimental Crystal Structure Determination
Related Article: Minna Kortelainen, Aku Suhonen, Andrea Hamza, Imre Pápai, Elisa Nauha, Sanna Yliniemelä-Sipari, Maija Nissinen, Petri M. Pihko|2015|Chem.-Eur.J.|21|9493|doi:10.1002/chem.201406521
CCDC 1022891: Experimental Crystal Structure Determination
Related Article: Aku Suhonen, Ian S. Morgan, Elisa Nauha, Kaisa Helttunen, Heikki M. Tuononen, Maija Nissinen|2015|Cryst.Growth Des.|15|2602|doi:10.1021/acs.cgd.5b00424
CCDC 1038222: Experimental Crystal Structure Determination
Related Article: Minna Kortelainen, Aku Suhonen, Andrea Hamza, Imre Pápai, Elisa Nauha, Sanna Yliniemelä-Sipari, Maija Nissinen, Petri M. Pihko|2015|Chem.-Eur.J.|21|9493|doi:10.1002/chem.201406521
CCDC 1552171: Experimental Crystal Structure Determination
Related Article: Kaisa Helttunen, Riia Annala, Aku Suhonen, Elisa Nauha, Juha Linnanto, Maija Nissinen|2017|CrystEngComm|19|5184|doi:10.1039/C7CE01109A
CCDC 1038221: Experimental Crystal Structure Determination
Related Article: Minna Kortelainen, Aku Suhonen, Andrea Hamza, Imre Pápai, Elisa Nauha, Sanna Yliniemelä-Sipari, Maija Nissinen, Petri M. Pihko|2015|Chem.-Eur.J.|21|9493|doi:10.1002/chem.201406521
CCDC 1022892: Experimental Crystal Structure Determination
Related Article: Aku Suhonen, Ian S. Morgan, Elisa Nauha, Kaisa Helttunen, Heikki M. Tuononen, Maija Nissinen|2015|Cryst.Growth Des.|15|2602|doi:10.1021/acs.cgd.5b00424
CCDC 1436674: Experimental Crystal Structure Determination
Related Article: Aku Suhonen, Minna Kortelainen, Elisa Nauha, Sanna Yliniemelä-Sipari, Petri M. Pihko, Maija Nissinen|2016|CrystEngComm|18|2005|doi:10.1039/C5CE02458G
CCDC 1552172: Experimental Crystal Structure Determination
Related Article: Kaisa Helttunen, Riia Annala, Aku Suhonen, Elisa Nauha, Juha Linnanto, Maija Nissinen|2017|CrystEngComm|19|5184|doi:10.1039/C7CE01109A
CCDC 1436667: Experimental Crystal Structure Determination
Related Article: Aku Suhonen, Minna Kortelainen, Elisa Nauha, Sanna Yliniemelä-Sipari, Petri M. Pihko, Maija Nissinen|2016|CrystEngComm|18|2005|doi:10.1039/C5CE02458G
CCDC 1552170: Experimental Crystal Structure Determination
Related Article: Kaisa Helttunen, Riia Annala, Aku Suhonen, Elisa Nauha, Juha Linnanto, Maija Nissinen|2017|CrystEngComm|19|5184|doi:10.1039/C7CE01109A
CCDC 1436665: Experimental Crystal Structure Determination
Related Article: Aku Suhonen, Minna Kortelainen, Elisa Nauha, Sanna Yliniemelä-Sipari, Petri M. Pihko, Maija Nissinen|2016|CrystEngComm|18|2005|doi:10.1039/C5CE02458G
CCDC 1552175: Experimental Crystal Structure Determination
Related Article: Kaisa Helttunen, Riia Annala, Aku Suhonen, Elisa Nauha, Juha Linnanto, Maija Nissinen|2017|CrystEngComm|19|5184|doi:10.1039/C7CE01109A
CCDC 1436670: Experimental Crystal Structure Determination
Related Article: Aku Suhonen, Minna Kortelainen, Elisa Nauha, Sanna Yliniemelä-Sipari, Petri M. Pihko, Maija Nissinen|2016|CrystEngComm|18|2005|doi:10.1039/C5CE02458G
CCDC 1038220: Experimental Crystal Structure Determination
Related Article: Minna Kortelainen, Aku Suhonen, Andrea Hamza, Imre Pápai, Elisa Nauha, Sanna Yliniemelä-Sipari, Maija Nissinen, Petri M. Pihko|2015|Chem.-Eur.J.|21|9493|doi:10.1002/chem.201406521
CCDC 1038217: Experimental Crystal Structure Determination
Related Article: Minna Kortelainen, Aku Suhonen, Andrea Hamza, Imre Pápai, Elisa Nauha, Sanna Yliniemelä-Sipari, Maija Nissinen, Petri M. Pihko|2015|Chem.-Eur.J.|21|9493|doi:10.1002/chem.201406521
CCDC 1436669: Experimental Crystal Structure Determination
Related Article: Aku Suhonen, Minna Kortelainen, Elisa Nauha, Sanna Yliniemelä-Sipari, Petri M. Pihko, Maija Nissinen|2016|CrystEngComm|18|2005|doi:10.1039/C5CE02458G
CCDC 1022889: Experimental Crystal Structure Determination
Related Article: Aku Suhonen, Ian S. Morgan, Elisa Nauha, Kaisa Helttunen, Heikki M. Tuononen, Maija Nissinen|2015|Cryst.Growth Des.|15|2602|doi:10.1021/acs.cgd.5b00424
CCDC 1436668: Experimental Crystal Structure Determination
Related Article: Aku Suhonen, Minna Kortelainen, Elisa Nauha, Sanna Yliniemelä-Sipari, Petri M. Pihko, Maija Nissinen|2016|CrystEngComm|18|2005|doi:10.1039/C5CE02458G
CCDC 1022890: Experimental Crystal Structure Determination
Related Article: Aku Suhonen, Ian S. Morgan, Elisa Nauha, Kaisa Helttunen, Heikki M. Tuononen, Maija Nissinen|2015|Cryst.Growth Des.|15|2602|doi:10.1021/acs.cgd.5b00424
CCDC 1436662: Experimental Crystal Structure Determination
Related Article: Aku Suhonen, Minna Kortelainen, Elisa Nauha, Sanna Yliniemelä-Sipari, Petri M. Pihko, Maija Nissinen|2016|CrystEngComm|18|2005|doi:10.1039/C5CE02458G
CCDC 1552173: Experimental Crystal Structure Determination
Related Article: Kaisa Helttunen, Riia Annala, Aku Suhonen, Elisa Nauha, Juha Linnanto, Maija Nissinen|2017|CrystEngComm|19|5184|doi:10.1039/C7CE01109A
CCDC 1552174: Experimental Crystal Structure Determination
Related Article: Kaisa Helttunen, Riia Annala, Aku Suhonen, Elisa Nauha, Juha Linnanto, Maija Nissinen|2017|CrystEngComm|19|5184|doi:10.1039/C7CE01109A
CCDC 1436673: Experimental Crystal Structure Determination
Related Article: Aku Suhonen, Minna Kortelainen, Elisa Nauha, Sanna Yliniemelä-Sipari, Petri M. Pihko, Maija Nissinen|2016|CrystEngComm|18|2005|doi:10.1039/C5CE02458G
CCDC 1038216: Experimental Crystal Structure Determination
Related Article: Minna Kortelainen, Aku Suhonen, Andrea Hamza, Imre Pápai, Elisa Nauha, Sanna Yliniemelä-Sipari, Maija Nissinen, Petri M. Pihko|2015|Chem.-Eur.J.|21|9493|doi:10.1002/chem.201406521
CCDC 1038223: Experimental Crystal Structure Determination
Related Article: Minna Kortelainen, Aku Suhonen, Andrea Hamza, Imre Pápai, Elisa Nauha, Sanna Yliniemelä-Sipari, Maija Nissinen, Petri M. Pihko|2015|Chem.-Eur.J.|21|9493|doi:10.1002/chem.201406521
CCDC 1436659: Experimental Crystal Structure Determination
Related Article: Aku Suhonen, Minna Kortelainen, Elisa Nauha, Sanna Yliniemelä-Sipari, Petri M. Pihko, Maija Nissinen|2016|CrystEngComm|18|2005|doi:10.1039/C5CE02458G
CCDC 1436672: Experimental Crystal Structure Determination
Related Article: Aku Suhonen, Minna Kortelainen, Elisa Nauha, Sanna Yliniemelä-Sipari, Petri M. Pihko, Maija Nissinen|2016|CrystEngComm|18|2005|doi:10.1039/C5CE02458G
CCDC 1436666: Experimental Crystal Structure Determination
Related Article: Aku Suhonen, Minna Kortelainen, Elisa Nauha, Sanna Yliniemelä-Sipari, Petri M. Pihko, Maija Nissinen|2016|CrystEngComm|18|2005|doi:10.1039/C5CE02458G
CCDC 1038215: Experimental Crystal Structure Determination
Related Article: Minna Kortelainen, Aku Suhonen, Andrea Hamza, Imre Pápai, Elisa Nauha, Sanna Yliniemelä-Sipari, Maija Nissinen, Petri M. Pihko|2015|Chem.-Eur.J.|21|9493|doi:10.1002/chem.201406521
CCDC 1038218: Experimental Crystal Structure Determination
Related Article: Minna Kortelainen, Aku Suhonen, Andrea Hamza, Imre Pápai, Elisa Nauha, Sanna Yliniemelä-Sipari, Maija Nissinen, Petri M. Pihko|2015|Chem.-Eur.J.|21|9493|doi:10.1002/chem.201406521
CCDC 1552169: Experimental Crystal Structure Determination
Related Article: Kaisa Helttunen, Riia Annala, Aku Suhonen, Elisa Nauha, Juha Linnanto, Maija Nissinen|2017|CrystEngComm|19|5184|doi:10.1039/C7CE01109A
CCDC 1552176: Experimental Crystal Structure Determination
Related Article: Kaisa Helttunen, Riia Annala, Aku Suhonen, Elisa Nauha, Juha Linnanto, Maija Nissinen|2017|CrystEngComm|19|5184|doi:10.1039/C7CE01109A
CCDC 1436664: Experimental Crystal Structure Determination
Related Article: Aku Suhonen, Minna Kortelainen, Elisa Nauha, Sanna Yliniemelä-Sipari, Petri M. Pihko, Maija Nissinen|2016|CrystEngComm|18|2005|doi:10.1039/C5CE02458G
CCDC 1436671: Experimental Crystal Structure Determination
Related Article: Aku Suhonen, Minna Kortelainen, Elisa Nauha, Sanna Yliniemelä-Sipari, Petri M. Pihko, Maija Nissinen|2016|CrystEngComm|18|2005|doi:10.1039/C5CE02458G
CCDC 1436661: Experimental Crystal Structure Determination
Related Article: Aku Suhonen, Minna Kortelainen, Elisa Nauha, Sanna Yliniemelä-Sipari, Petri M. Pihko, Maija Nissinen|2016|CrystEngComm|18|2005|doi:10.1039/C5CE02458G