Glycoluril–tetrathiafulvalene molecular clips: on the influence of electronic and spatial properties for binding neutral accepting guests

• Yoann Cotelle,
• Marie Hardouin-Lerouge,
• Stéphanie Legoupy,
• Olivier Alévêque,
• Eric Levillain and
• Piétrick Hudhomme

Beilstein J. Org. Chem. 2015, 11, 1023–1036, doi:10.3762/bjoc.11.115

• isolated in around 20% yield. Whereas all attempts at growing crystals of molecular clips 1 and 4 of sufficient quality for X-ray analysis have been unsuccessful so far, suitable single crystals were obtained by slow diffusion from a solution of clips 2 and 3 in a CH2Cl2/hexane mixture. Considering the

• ). This typical packing arrangement was previously observed in many cases of glycoluril-based molecular clips containing two aromatic sidewalls [26][60][61][62][63]. On the contrary, considering the unit cell for single crystals of clip 2, X-ray analysis showed that two neighboring molecules of clip 2

Tuning the size of a redox-active tetrathiafulvalene-based self-assembled ring

• Sébastien Bivaud,
• Sébastien Goeb,
• Vincent Croué,
• Magali Allain,
• Flavia Pop and
• Marc Sallé

Beilstein J. Org. Chem. 2015, 11, 966–971, doi:10.3762/bjoc.11.108

• +, [M6L3-8TfO−]4+, [M6L3-7TfO−]5+ species and matching perfectly with theoretical ones (Supporting Information File 1, Figure S8). Single crystals of assembly M6L3 were grown by slow diffusion of ethyl acetate in DMSO and allowed for determining unambiguously the solid-state structure by a synchrotron X

Synthesis and characterization of the cyanobenzene-ethylenedithio-TTF donor

• Sandrina Oliveira,
• Dulce Belo,
• Isabel C. Santos,
• Sandra Rabaça and
• Manuel Almeida

Beilstein J. Org. Chem. 2015, 11, 951–956, doi:10.3762/bjoc.11.106

• expected for the seven protons. Single crystals of 3 suitable for X-ray analysis were grown by slow evaporation from a dichloromethane solution. The X-ray structural refinement confirm the molecular structure of the compound 3 and was found to crystallize in the monoclinic system, space group P21/n with

Copper ion salts of arylthiotetrathiafulvalenes: synthesis, structure diversity and magnetic properties

• Longfei Ma,
• Jibin Sun,
• Xiaofeng Lu,
• Shangxi Zhang,
• Hui Qi,
• Lei Liu,
• Yongliang Shao and
• Xiangfeng Shao

Beilstein J. Org. Chem. 2015, 11, 850–859, doi:10.3762/bjoc.11.95

• . Crystal structure The single crystals for all of the present salts were suitable for the X-ray single crystal diffraction analyses. Herein, we report the crystal structures of the typical salts (Figures 1–5), and those of the others are supplied in Supporting Information File 1. As mentioned above, the

Self-assembly of heteroleptic dinuclear metallosupramolecular kites from multivalent ligands via social self-sorting

• Christian Benkhäuser and
• Arne Lützen

Beilstein J. Org. Chem. 2015, 11, 693–700, doi:10.3762/bjoc.11.79

• . Unfortunately, we were not able to grow suitable single crystals of this complex that could be analyzed by X-ray diffraction. Nevertheless the experimental evidence provided by the NMR and MS investigations clearly indicate the formation of the desired heteroleptic complex [Cu2(1)(2)](BF4)2 in racemic form

Trifluoromethyl-substituted tetrathiafulvalenes

• Olivier Jeannin,
• Frédéric Barrière and
• Marc Fourmigué

Beilstein J. Org. Chem. 2015, 11, 647–658, doi:10.3762/bjoc.11.73

• )(FeCl4), polluted with the yellow crystals of (Et4N)(FeCl4). Crystallography Single crystals were mounted on the top of a thin glass fiber. Data were collected either on a Stoe-IPDS at room temperature or on a Nonius KappaCCD diffractometer at 150 K, both equipped with graphite-monochromated Mo Kα

TTFs nonsymmetrically fused with alkylthiophenic moieties

• Rafaela A. L. Silva,
• Bruno J. C. Vieira,
• Marta M. Andrade,
• Isabel C. Santos,
• Sandra Rabaça,
• Dulce Belo and
• Manuel Almeida

Beilstein J. Org. Chem. 2015, 11, 628–637, doi:10.3762/bjoc.11.71

• acceptable yield of 28% for 1 and a very good yield of 63% for 2 could be obtained after purification through column chromatography, eluting with dichloromethane. The new TTF-type donors are soluble in commonly used organic solvents, such as CH2Cl2, CHCl3, acetonitrile and n-hexane. Single crystals suitable

• CH2Cl2 (Rf = 0.47). Single crystals were obtained by slow evaporation of a chloroform solution of 1. Yield: 28% (176 mg); Anal. calcd for C18H18N2S7: C, 44.41; H, 3.72; N, 5.75; S, 46.11; found: C, 44.53; H, 4.00; N, 5.17; S, 46.33; FTIR (KBr): 2960 (m, –CH2–), 2252 (m, –C≡N), 1634 (m, C=C), 1423 (S, S

The preparation of new functionalized [2.2]paracyclophane derivatives with N-containing functional groups

• Henning Hopf,
• Swaminathan Vijay Narayanan and
• Peter G. Jones

Beilstein J. Org. Chem. 2015, 11, 437–445, doi:10.3762/bjoc.11.50

• most other acyl chlorides, 26 is a stable compound with a high melting point (210 °C), which could easily be recrystallized from dichloromethane/pentane to furnish single crystals suitable for X-structural analysis. The molecule of 26 (Figure 5) possesses crystallographic inversion symmetry, consistent

Attempts to prepare an all-carbon indigoid system

• Şeref Yildizhan,
• Henning Hopf and
• Peter G. Jones

Beilstein J. Org. Chem. 2015, 11, 363–372, doi:10.3762/bjoc.11.42

• refrigerator for longer periods of time without decomposition. Slow evaporation of the solvent of a chloroform solution provided single crystals of 13 that were suitable for X-ray structure analysis. The resulting structure is shown in Figure 1. Compound 13 crystallizes with two independent but closely similar

• . To distinguish between these two possibilities based on spectroscopic evidence alone would not be easy. Fortunately, however, single crystals of the isolated dimer, suitable for X-ray analysis, were obtained, showing unambiguously that the anti-orientation is preferred (Figure 2). The molecule of 17

• structure determination had to await X-ray crystallographic analysis. The required single crystals were obtained from the different chromatographic fractions (which contained either isomer in enriched form only) by recrystallization from chloroform and dichloromethane/chloroform, respectively. As can be

IR and electrochemical synthesis and characterization of thin films of PEDOT grown on platinum single crystal electrodes in [EMMIM]Tf₂N ionic liquid

• Andrea P. Sandoval,
• Marco F. Suárez-Herrera and
• Juan M. Feliu

Beilstein J. Org. Chem. 2015, 11, 348–357, doi:10.3762/bjoc.11.40

• reaction of PEDOT were studied using in situ FTIR spectroscopy. Keywords: AFM; [EMMIM]Tf2N ionic liquid; in situ IR; PEDOT; Pt single crystals; Introduction Conducting polymers have been subject of an intense research during the last decades because they exhibit high conductivity and interesting optical

• of the polymer is less probable and the average length of the polymer chains is higher in ionic liquids than in molecular solvents [15]. In this work, Pt single crystals electrodes and the moisture stable IL 1-ethyl-2,3-dimethylimidazolium triflimide, [EMMIM]Tf2N [16], are used to carry out the

• on the nature and number of charge carriers take place. Experimental The electrochemical experiments were performed in single compartment glass cells. A platinum wire was used as counter electrode, and a silver wire was used as the pseudoreference electrode. Platinum single crystals were used as

Inclusion of trans-resveratrol in methylated cyclodextrins: synthesis and solid-state structures

• Lee Trollope,
• Dyanne L. Cruickshank,
• Terence Noonan,
• Susan A. Bourne,
• Milena Sorrenti,
• Laura Catenacci and
• Mino R. Caira

Beilstein J. Org. Chem. 2014, 10, 3136–3151, doi:10.3762/bjoc.10.331

• inclusion compounds as single crystals enabled their complete structural elucidation, revealing several novel supramolecular features which are relevant for future studies of the antioxidant RSV. Availability of well-defined, crystalline inclusion complexes also ensured that their characterization using

• , suggesting its inclusion in the cavity of DMB. It is noted that the DSC trace from ground single crystals of the phase later identified as the inclusion complex DMB·RSV·4H2O instead showed different features from those reported above for DMB–RSV combinations, the most prominent endotherm appearing at ca. 233

• high-quality single crystals of each of the three inclusion complexes. The host–guest stoichiometries of the inclusion complexes between RSV and the three methylated CDs were all found to be 1:1 from 1H NMR spectra of solutions of single crystals of the respective complexes (Supporting Information File

The unexpected influence of aryl substituents in N-aryl-3-oxobutanamides on the behavior of their multicomponent reactions with 5-amino-3-methylisoxazole and salicylaldehyde

• Volodymyr V. Tkachenko,
• Elena A. Muravyova,
• Sergey M. Desenko,
• Oleg V. Shishkin,
• Svetlana V. Shishkina,
• Dmytro O. Sysoiev,
• Thomas J. J. Müller and
• Valentin A. Chebanov

Beilstein J. Org. Chem. 2014, 10, 3019–3030, doi:10.3762/bjoc.10.320

• Volodymyr V. Tkachenko Elena A. Muravyova Sergey M. Desenko Oleg V. Shishkin Svetlana V. Shishkina Dmytro O. Sysoiev Thomas J. J. Muller Valentin A. Chebanov Division of Chemistry of Functional Materials, SSI “Institute for Single Crystals” NAS of Ukraine, Lenin Ave. 60, Kharkiv 61001, Ukraine

A new approach for the synthesis of bisindoles through AgOTf as catalyst

• Jorge Beltrá,
• M. Concepción Gimeno and
• Raquel P. Herrera

Beilstein J. Org. Chem. 2014, 10, 2206–2214, doi:10.3762/bjoc.10.228

• clean crude product was obtained since acetaldehyde is also evaporated, and the final product was purified by a simple column chromatography. Moreover, we were able to obtain single crystals for compounds 6ad and 6al for the first time in the literature (Figure 2) [50]. Although the mechanism is not

Scalable synthesis of 5,11-diethynylated indeno[1,2-b]fluorene-6,12-diones and exploration of their solid state packing

• Bradley D. Rose,
• Peter J. Santa Maria,
• Aaron G. Fix,
• Chris L. Vonnegut,
• Lev N. Zakharov,
• Sean R. Parkin and
• Michael M. Haley

Beilstein J. Org. Chem. 2014, 10, 2122–2130, doi:10.3762/bjoc.10.219

• pentacene, as it, along with numerous other acene derivatives, has been substituted with trialkylsilylethynyl groups of varying size to study the effect on the solid state packing in single crystals [17]. This was shown to have a large effect on the OFET performance as slight changes in the geometry can

• silyl groups. The high crystallinity of the majority of the compounds examined permitted facile growth of large single crystals, of approximately several millimeters, from hexanes solution. Single crystals for 8g and 8j were grown from chlorobenzene due to the low solubility and crystallinity of these

• , which are dominated by the conjugated core; however, there were marked differences in the solid-state packing of single crystals of these compounds. Unfortunately, from a zeroth order approximation none of the variants displayed promising intermolecular electronic coupling. Previously reported indeno

Five-membered ring annelation in [2.2]paracyclophanes by aldol condensation

• Henning Hopf,
• Swaminathan Vijay Narayanan and
• Peter G. Jones

Beilstein J. Org. Chem. 2014, 10, 2021–2026, doi:10.3762/bjoc.10.210

• , and also furnishes three dehydration products, the anti-configurated diketones 21–23, produced in a 1:3:1 ratio. Again the fully or partially conjugated isomers are deeply colored (intense yellow) and display absorption maxima at 389 and 358 nm, respectively (Scheme 6). For 21 yellow single crystals

Building complex carbon skeletons with ethynyl[2.2]paracyclophanes

• Ina Dix,
• Lidija Bondarenko,
• Peter G. Jones,
• Thomas Oeser and
• Henning Hopf

Beilstein J. Org. Chem. 2014, 10, 2013–2020, doi:10.3762/bjoc.10.209

• recrystallized to provide single crystals suitable for X-ray structural analysis. Figure 1 shows that dimer 11 indeed possesses the “crossed” structure; it crystallizes with imposed twofold symmetry, but the effective (non-crystallographic) symmetry is the unusual D2 (222) with r.m.s. deviation 0.01 Å. Despite

Reaction of selected carbohydrate aldehydes with benzylmagnesium halides: benzyl versus o-tolyl rearrangement

• Maroš Bella,
• Bohumil Steiner,
• Vratislav Langer and
• Miroslav Koóš

Beilstein J. Org. Chem. 2014, 10, 1942–1950, doi:10.3762/bjoc.10.202

• of CH3 protons of the o-tolyl moiety, indicating that the benzyl→o-tolyl rearrangement did not occur in these cases; accordingly, no further detailed inspections of the reaction mixtures were performed. X-ray analysis Single crystals (stable at ambient temperature) suitable for X-ray diffraction were

Macrocyclic bis(ureas) as ligands for anion complexation

• Claudia Kretschmer,
• Gertrud Dittmann and
• Johannes Beck

Beilstein J. Org. Chem. 2014, 10, 1834–1839, doi:10.3762/bjoc.10.193

• in good yields. The quest for the molecular conformation is challenging for both molecules. Since the bis(triazenide) congeners of 1 and 2 are planar, one can presume an analogous molecular shape for the bis(ureas). All attempts to obtain single crystals of 1 for a structure determination failed

One-pot stereoselective synthesis of α,β-differentiated diamino esters via the sequence of aminochlorination, aziridination and intermolecular S_N2 reaction

• Yiwen Xiong,
• Ping Qian,
• Chenhui Cao,
• Haibo Mei,
• Jianlin Han,
• Guigen Li and
• Yi Pan

Beilstein J. Org. Chem. 2014, 10, 1802–1807, doi:10.3762/bjoc.10.189

• the steric hindrance affects the formation of the product. Furthermore, excellent stereoselectivity was obtained for all of the examined cinnamic ester substrates, and only the anti-isomers were observed. To determine the structure of product 5, single crystals were prepared. Fortunately, the crystals

Aryl substitution of pentacenes

• Andreas R. Waterloo,
• Anna-Chiara Sale,
• Dan Lehnherr,
• Frank Hampel and
• Rik R. Tykwinski

Beilstein J. Org. Chem. 2014, 10, 1692–1705, doi:10.3762/bjoc.10.178

• acenes can provide vital information about intermolecular interactions, single crystals of pentacenes 3a–d and 3g–j were grown and their solid-state arrangements determined by single crystal X-ray diffraction analysis (crystallographic details are provided in Supporting Information File 1). Pentacene 3a

Aza-Diels–Alder reaction between N-aryl-1-oxo-1H-isoindolium ions and tert-enamides: Steric effects on reaction outcome

• Amitabh Jha,
• Ting-Yi Chou,
• Zainab ALJaroudi,
• Bobby D. Ellis and
• T. Stanley Cameron

Beilstein J. Org. Chem. 2014, 10, 848–857, doi:10.3762/bjoc.10.81

• crystallography on single crystals of the three representative compounds 1b, 1h and 2b (CCDC 952236, 951754 and 951755 respectively). Their ORTEP diagrams and corresponding 2D structures of these compounds are shown in Figure 2. 1H and 13C NMR spectra of all isolated products also indicate formation of a single

Dimerisation, rhodium complex formation and rearrangements of N-heterocyclic carbenes of indazoles

• Zong Guan,
• Jan C. Namyslo,
• Martin H. H. Drafz,
• Martin Nieger and
• Andreas Schmidt

Beilstein J. Org. Chem. 2014, 10, 832–840, doi:10.3762/bjoc.10.79

• strong donor strengths of these indazol-3-ylidenes as already postulated earlier on comparing different stretching frequencies of selected 5-membered NHCs [27] or 13C NMR resonance frequencies of several palladium carbene complexes [28]. We were able to obtain single crystals of 15e to perform an X-ray

• analysis (Figure 3). Suitable single crystals were obtained by slow evaporation of a concentrated solution in dichloromethane/iPrOH. The complex crystallized monoclinic. The Rh–Ccarbene and Rh–CCO bond lengths [Rh1–C1 and Rh1–C10; crystallographic numbering] were determined to be 206.0(2) pm and 186.3(3

• ). The mechanism can be rationalized by formation of an ylide by 1,7-H-shift from the mesomeric betaine III, followed by ring cleavage of the indazole ring and subsequent ring-closure of the resulting 1,6-dipole to give the quinazolines 16a–d. Single crystals of 16b suitable for an X-ray analysis were

Self-assembly of metallosupramolecular rhombi from chiral concave 9,9’-spirobifluorene-derived bis(pyridine) ligands

• Rainer Hovorka,
• Sophie Hytteballe,
• Torsten Piehler,
• Georg Meyer-Eppler,
• Filip Topić,
• Kari Rissanen,
• Marianne Engeser and
• Arne Lützen

Beilstein J. Org. Chem. 2014, 10, 432–441, doi:10.3762/bjoc.10.40

• compared to the ratios obtained by other techniques, e.g. NMR spectroscopy, as we have recently reported [28]. Finally, we were able to grow single crystals of the dinuclear palladium complexes derived from the racemic ligands from a 3:1 mixture of dichloromethane and acetonitrile using ethyl acetate as

• anti-solvent and characterise them by X-ray diffraction. Interestingly, we only obtained single crystals of the racemic mixture of homochiral complexes although the solution obviously contains both diastereomers. Figure 5 shows both of the homochiral complexes {[(dppp)2Pd2{(R)-3}2](OTf)4 and {[(dppp

Intermediates in monensin biosynthesis: A late step in biosynthesis of the polyether ionophore monensin is crucial for the integrity of cation binding

• Wolfgang Hüttel,
• Jonathan B. Spencer and
• Peter F. Leadlay

Beilstein J. Org. Chem. 2014, 10, 361–368, doi:10.3762/bjoc.10.34

• monensin derivatives in excellent yields (ΔmonD: 1.13 g L−1 dehydroxymonensin; ΔmonE: 0.50 g L−1 demethylmonensin; and double mutant ΔmonDΔmonE: 0.34 g L−1 dehydroxydemethylmonensin). Single crystals were obtained from purified fractions of dehydroxymonensin and demethylmonensin. X-ray structure analysis

• crystallised as their monosodium salts from an isohexane/ethyl acetate mixture and single crystals were subjected to X-ray structural analysis (Figure 2). Dehydroxydemethylmonensin A did not form crystals under any conditions tested. When the demethylmonensin A structure is overlaid on the structure of the

The regioselective synthesis of spirooxindolo pyrrolidines and pyrrolizidines via three-component reactions of acrylamides and aroylacrylic acids with isatins and α-amino acids

• Tatyana L. Pavlovskaya,
• Fedor G. Yaremenko,
• Victoria V. Lipson,
• Svetlana V. Shishkina,
• Oleg V. Shishkin,
• Vladimir I. Musatov and
• Alexander S. Karpenko

Beilstein J. Org. Chem. 2014, 10, 117–126, doi:10.3762/bjoc.10.8

• Tatyana L. Pavlovskaya Fedor G. Yaremenko Victoria V. Lipson Svetlana V. Shishkina Oleg V. Shishkin Vladimir I. Musatov Alexander S. Karpenko State Scientific Institution “Institute for Single Crystals” of National Academy of Sciences of Ukraine, 60, Lenin ave., Kharkov, 61178, Ukraine