Ring-whizzing in polyene-PtL₂ complexes revisited

• Oluwakemi A. Oloba-Whenu,
• Thomas A. Albright and
• Chirine Soubra-Ghaoui

Beilstein J. Org. Chem. 2016, 12, 1410–1420, doi:10.3762/bjoc.12.135

• over the face of the cyclopropenium ring [36]. These structures serve to chart this reaction path and this is consistent with a small reaction barrier with the resultant structure being determined by crystal packing effects. The details have been reported previously [21][36]. The optimizations reveal

Indenopyrans – synthesis and photoluminescence properties

• Andreea Petronela Diac,
• Ana-Maria Ţepeş,
• Albert Soran,
• Ion Grosu,
• Anamaria Terec,
• Jean Roncali and
• Elena Bogdan

Beilstein J. Org. Chem. 2016, 12, 825–834, doi:10.3762/bjoc.12.81

• the (C19–24) ring, respectively (Figure 6a). Several weak, intermolecular C–H···O hydrogen bonds could be identified in the crystal packing (Table S1, Supporting Information File 1). Although the H···O distances are close to or greater than the van der Waals limit of 2.60 Å [39], they are still within

• interactions. Further edge-to-face H···π [44] and π–π interactions [45][46] (Table 4) between molecules from neighboring layers contribute to the three-dimensional crystal packing (Figure S6 in Supporting Information File 1). Conclusion Several indenopyrone derivatives were synthesized and characterized by NMR

Inclusion complexes of 2-methoxyestradiol with dimethylated and permethylated β-cyclodextrins: models for cyclodextrin–steroid interaction

• Mino R. Caira,
• Susan A. Bourne,
• Halima Samsodien and
• Vincent J. Smith

Beilstein J. Org. Chem. 2015, 11, 2616–2630, doi:10.3762/bjoc.11.281

• presence of four TRIMEB·2ME units (A–D) in the asymmetric unit. Table 1 summarises the crystal data and refinement details for the two complexes. Salient features of the mode of inclusion of the steroid molecule 2ME in the host DIMEB molecule and complex crystal packing are shown in Figure 2. In the

• inclusion of the 2ME molecule in the host DIMEB. Protrusion of the A-ring of the 2ME molecule from the secondary side of the DIMEB host molecule leads to a unique crystal packing arrangement, details of which are shown in Figure 2d–f. The A-ring of the 2ME molecule in the central complex unit (Figure 2d) is

Friedel–Crafts-type reaction of pyrene with diethyl 1-(isothiocyanato)alkylphosphonates. Efficient synthesis of highly fluorescent diethyl 1-(pyrene-1-carboxamido)alkylphosphonates and 1-(pyrene-1-carboxamido)methylphosphonic acid

• Anna Wrona-Piotrowicz,
• Janusz Zakrzewski,
• Anna Gajda,
• Tadeusz Gajda,
• Anna Makal,
• Arnaud Brosseau and
• Rémi Métivier

Beilstein J. Org. Chem. 2015, 11, 2451–2458, doi:10.3762/bjoc.11.266

• an X-ray diffraction study (vide infra). Molecular structure, crystal packing and solid-state fluorescence of 3a Compound 3a crystallized from layered dichloromethane–hexane in the monoclinic space group P21/c, with a single molecule occupying an asymmetric unit in general position. Its molecular

• , apart from the H1 atom which was involved in intermolecular hydrogen bond formation. (a) Dimers of π-stacked and hydrogen-bonded molecules of 3a represented in single figures; (b) network of weak C–H…O and C–H…π interactions stabilizing H-bonded dimer strings and (c) crystal packing along the

Investigation of the role of stereoelectronic effects in the conformation of piperidones by NMR spectroscopy and X-ray diffraction

• Cesar Garcias-Morales,
• David Ortegón-Reyna and
• Armando Ariza-Castolo

Beilstein J. Org. Chem. 2015, 11, 1973–1984, doi:10.3762/bjoc.11.213

• diagram of 1. The thermal ellipsoids are drawn at the 30% probability level for all atoms other than H. (b) Crystal packing and N(3)–H(3)∙∙∙O(1) intermolecular hydrogen bonds of 1. (a) ORTEP diagrams of 6 and 7. The thermal ellipsoids are drawn at the 30% probability level for all atoms other than H. (b

Consequences of the electronic tuning of latent ruthenium-based olefin metathesis catalysts on their reactivity

• Karolina Żukowska,
• Eva Pump,
• Aleksandra E. Pazio,
• Krzysztof Woźniak,
• Luigi Cavallo and
• Christian Slugovc

Beilstein J. Org. Chem. 2015, 11, 1458–1468, doi:10.3762/bjoc.11.158

• -ray diffraction. Each of them includes two molecules of the studied compound in the trans-conformation and one molecule of the solvent (dichloromethane) in the asymmetric part of the unit cell (Figure 2). Both crystals are isotypic, so the crystal packing is identical and lattice dimensions are very

Tetrathiafulvalene-based azine ligands for anion and metal cation coordination

• Awatef Ayadi,
• Aziz El Alamy,
• Olivier Alévêque,
• Magali Allain,
• Nabil Zouari,
• Mohammed Bouachrine and
• Abdelkrim El-Ghayoury

Beilstein J. Org. Chem. 2015, 11, 1379–1391, doi:10.3762/bjoc.11.149

• : 794.8787; found: 794.8781. Crystal structure of ligand L1 with atom numbering scheme (top) and a side view of the molecule (bottom). Partial crystal packing of ligand L1 with formation of head to tail dimers that stack along a-axis forming columns that are connected through hydrogen bonding along c-axis

Tuning of tetrathiafulvalene properties: versatile synthesis of N-arylated monopyrrolotetrathiafulvalenes via Ullmann-type coupling reactions

• Vladimir A. Azov,
• Diana Janott,
• Dirk Schlüter and
• Matthias Zeller

Beilstein J. Org. Chem. 2015, 11, 860–868, doi:10.3762/bjoc.11.96

• direct conjugation with the tetrathiafulvalene chromophore. The crystal packing of the arylated monopyrrolotetrathiafulvalenes is primarily defined by networks of C–H···X weak hydrogen bonds and short S···S contacts involving the tetrathiafulvalene moieties. Keywords: cyclic voltammetry; N-arylation

• -parallel tilted edge-to face arrangements. In the crystal packing, molecules are interconnected by multiple non-classical weak intermolecular hydrogen bonds [31] and C–H···π and S···S interactions, the latter being common in the crystals of sulfur-rich compounds such as TTFs [32]. Most of the close

• ; CH2Cl2/0.1 M Bu4NClO4). Crystal packing of 4a viewed along the a axis and showing one layer of molecules. Short S···S contacts are shown as black and S···C contacts as green dashed lines. Only the major orientation of the disordered propyl chain is shown. Crystal packing of 4b showing a group of four

Anionic sigmatropic-electrocyclic-Chugaev cascades: accessing 12-aryl-5-(methylthiocarbonylthio)tetracenes and a related anthra[2,3-b]thiophene

• Laurence Burroughs,
• John Ritchie,
• Mkhethwa Ngwenya,
• Dilfaraz Khan,
• William Lewis and
• Simon Woodward

Beilstein J. Org. Chem. 2015, 11, 273–279, doi:10.3762/bjoc.11.31

• molecular connectivity but more importantly allowed insight into their crystal packing features (Scheme 5 and Supporting Information File 1) across the family of structures. Pairs of 7a associate with slip-stack pairing (Cπ···Cπ 3.51–3.72 Å). Each of these (7a)2 ‘dimers’ is linked to the next through π

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

• , permethylated β-CD and 2,6-dimethylated β-CD) are described. Isolation of the corresponding crystalline 1:1 inclusion compounds enabled their full structure determination by X-ray analysis for the first time, revealing a variety of guest inclusion modes and unique supramolecular crystal packing motifs. The

• presence of guest disorder in two cases. An account of the key features of the inclusion of the RSV molecule within the respective host cavities as well as descriptions of the crystal packing arrangements follows. The asymmetric unit of the complex TMA·RSV·6.25H2O, namely two TMA molecules, two RSV

• as well as numerous water–water O–H···O hydrogen bonds. The crystal packing is shown in Figure 15. Complex units stack in columns parallel to the a-axis in a head-to-tail fashion with (as noted above) a small extent of host self-inclusion (Figure 15a). Figure 15b illustrates the modified herringbone

Preparation and evaluation of cyclodextrin polypseudorotaxane with PEGylated liposome as a sustained release drug carrier

• Kayoko Hayashida,
• Taishi Higashi,
• Daichi Kono,
• Keiichi Motoyama,
• Koki Wada and
• Hidetoshi Arima

Beilstein J. Org. Chem. 2014, 10, 2756–2764, doi:10.3762/bjoc.10.292

• -CD system (Figure 3A). This shift is probably caused by the hydrogen bonds of the O–H groups of γ-CD derived from PPRX formation [43]. There are three types of crystal packing of CD complexes, namely, the channel type, the cage type and the layer structure [44]. The powder X-ray diffractograms are

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

• gram amounts of material. With this new methodology, we explored the effects on crystal packing morphology for the indeno[1,2-b]fluorene-6,12-diones by varying the substituents on the silylethynyl groups. Keywords: crystal packing; electron accepting; indenofluorenes; organic electronics; polycyclic

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

• bridge angles and narrowed sp2 ring angles at the bridgehead atoms, and boat-shaped six-membered rings with the bridgehead atoms lying out of the plane of the other four atoms (see Table 2 below). The crystal packing involves two classical and three "weak" hydrogen bonds (two involving the

Substitution effect and effect of axle’s flexibility at (pseudo-)rotaxanes

• Friedrich Malberg,
• Jan Gerit Brandenburg,
• Werner Reckien,
• Oldamur Hollóczki,
• Stefan Grimme and
• Barbara Kirchner

Beilstein J. Org. Chem. 2014, 10, 1299–1307, doi:10.3762/bjoc.10.131

• angles differ by less than 0.3° from the X-ray structure. Because the molecular structure is rather flexible, we observe interesting crystal packing effects. We compared the highlighted intramolecular distances and angles from experiment and theory in Figure 2. As a result, we exemplified the influence

• less than 2%. However, care has to be taken when comparing results calculated in the gas phase with those obtained in the condensed phase due to non-local crystal packing effects. The computed DFT-D3 formation energies of the non-covalently bound rotaxanes in the gas phase range from about −41 to −58

Columnar/herringbone dual crystal packing of pyrenylsumanene and its photophysical properties

• Binod Babu Shrestha,
• Shuhei Higashibayashi and
• Hidehiro Sakurai

Beilstein J. Org. Chem. 2014, 10, 841–847, doi:10.3762/bjoc.10.80

• Science, Myodaiji, Okazaki, Aichi 444-8787, Japan, Japan Science and Technology Agency, ACT-C, 4-1-8 Honcho, Kawaguchi, Saitama 332-0012, Japan 10.3762/bjoc.10.80 Abstract A single crystal of pyrenylsumanene was found to exhibit both columnar and herringbone crystal packing. The sumanene moieties form

• emission with high quantum yield (0.82) was observed for pyrenylsumanene in solution, while excimer-type red-shifted emission was evident in the crystalline phase. Keywords: carbon nanomaterials; columnar crystal packing; fluorescence; herringbone; pyrenylsumanene; Introduction Buckybowls – bowl-shaped

• favour a herringbone packing structure (Figure 1c) due to π–π and CH–π interactions [19][20]. To date, buckybowl derivatives with planar aromatic substituents have not been well studied and thus we wished to examine the crystal packing modes and solid-state properties of dual-nature compounds

Use of activated enol ethers in the synthesis of pyrazoles: reactions with hydrazine and a study of pyrazole tautomerism

• Denisa Tarabová,
• Stanislava Šoralová,
• Martin Breza,
• Marek Fronc,
• Wolfgang Holzer and
• Viktor Milata

Beilstein J. Org. Chem. 2014, 10, 752–760, doi:10.3762/bjoc.10.70

• established by NMR. A tautomer C with an azine (C=N–N=C) structure has not been observed. Tautomers of 5a. Tautomers of 5b (R = Me), 5c (R = Et). Tautomers of 5b (R = Me), 5c (R = Et). Tautomers of 5d. Crystal structure and crystal packing of compound 6a. Key 1H (red), 13C (black) and 15N (blue) NMR chemical

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

• solvent molecules within the crystal packing, and hydrogen atoms are omitted, colour code: petrol – palladium, grey – carbon, blue – nitrogen, orange – phosphorous). Synthesis of ligands 3 and 6. Supporting Information Supporting Information File 242: NMR and ESI mass spectra of ligands 3 and 6 and their

Crystal design using multipolar electrostatic interactions: A concept study for organic electronics

• Peer Kirsch,
• Qiong Tong and
• Harald Untenecker

Beilstein J. Org. Chem. 2013, 9, 2367–2373, doi:10.3762/bjoc.9.272

• electrostatically controlled crystal packing is the very poor solubility of 1. Theoretical study on electronic properties In order to explore the potential utility of 1 and its analogues as an organic semiconductor, the transfer integrals [20][21] for hole and electron transfer between the four closest pairs of

• ). Although the control of the crystal packing by “sculpting” the electrostatic potential surface is demonstrated impressively, also the drawback of the concept becomes visible: the same intermolecular electrostatic forces which shape and stabilize the crystal packing cause extremely poor solubility and

Isolation and X-ray characterization of palladium–N complexes in the guanylation of aromatic amines. Mechanistic implications

• Abdessamad Grirrane,
• Hermenegildo Garcia and
• Eleuterio Álvarez

Beilstein J. Org. Chem. 2013, 9, 1455–1462, doi:10.3762/bjoc.9.165

• were fully characterized by analytical and spectroscopic data (see Supporting Information File 1, experimental section). Structure of guanidine 5a was confirmed by single-crystal X-ray analysis, Figure 4 shows the corresponding ORTEP for compound 5a as well as some views of the crystal packing (see

• ) Crystal packing detail of 4a viewed along the a-axis showing the presence of inter- and intramolecular hydrogen bonds between Cl and H (NH groups) atoms. (Left) ORTEP representation of 4b. (Right) Crystal packing detail of 4b viewed along the a-axis showing the presence of intermolecular hydrogen bonds

• between O (from the dioxole moieties) and N (NH groups) atoms. (Left) ORTEP representation of 4c. (Right) Crystal-packing detail of 4c viewed along the a-axis showing the presence of intermolecular hydrogen bonds between Cl and N (NH groups) atoms. (Left) ORTEP representation of 5a. (Right) Crystal

Ring-opening reaction of 2,5-dioctyldithieno[2,3-b:3',2'-d]thiophene in the presence of aryllithium reagents

• Hao Zhong,
• Jianwu Shi,
• Jianxun Kang,
• Shaomin Wang,
• Xinming Liu and
• Hua Wang

Beilstein J. Org. Chem. 2013, 9, 767–774, doi:10.3762/bjoc.9.87

• ) of 55.4° and a dihedral angle of 56.1°. The pyrenylsulfanyl group is not coplanar to the neighboring thiophene ring with a dihedral angle of 79.5° and a torsion angle (C5–C6–S2–C10) of 89.7°. There are short contacts of hydrogen bonding found in the crystal packing. However, no π–π interaction was

• , 31.83, 31.81, 31.27, 31.22, 30.53, 29.92, 29.71, 29.28, 29.21, 29.15, 29.06, 28.52, 22.66, 22.62, 22.39, 14.11, 13.79; IR (KBr): 3435 (Ar-H), 2956, 2924, 2855 (C-H) cm−1; HRMS–EI m/z: [M]+ calcd for C44H54S3, 678.3392; found, 678.3382. Crystallographic structure of 3i (left, top view) and crystal

• packing (right). Carbon, silicon, oxygen and sulfur atoms are depicted with thermal ellipsoids set at 50% probability level, and all hydrogen atoms are omitted for clarity. The ring-opening reaction of symmetric 2,5-disubstituted-dithieno[2,3-b:3',2'-d]thiophenes in the presence of n-BuLi in THF. The ring

Spin state switching in iron coordination compounds

• Philipp Gütlich,
• Ana B. Gaspar and
• Yann Garcia

Beilstein J. Org. Chem. 2013, 9, 342–391, doi:10.3762/bjoc.9.39

Inclusion of the insecticide fenitrothion in dimethylated-β-cyclodextrin: unusual guest disorder in the solid state and efficient retardation of the hydrolysis rate of the complexed guest in alkaline solution

• Dyanne L. Cruickshank,
• Natalia M. Rougier,
• Raquel V. Vico,
• Susan A. Bourne,
• Elba I. Buján,
• Mino R. Caira and
• Rita H. de Rossi

Beilstein J. Org. Chem. 2013, 9, 106–117, doi:10.3762/bjoc.9.14

• molecules and there are no close contacts between the disordered guest molecules and host molecules. Figure 7 shows space-filling diagrams that illustrate representative modes of guest inclusion. Crystal packing is shown in Figure 8. The complex units stack head-to-tail in infinite columns parallel to the x

The crystal structure of the Dess–Martin periodinane

• Albert Schröckeneder,
• Desiree Stichnoth,
• Peter Mayer and
• Dirk Trauner

Beilstein J. Org. Chem. 2012, 8, 1523–1527, doi:10.3762/bjoc.8.172

• significantly different bond lengths (I1–O5 = 2.0670(13) Å, I1–O7 = 2.1141(13) Å), which desymmetrizes the molecule overall. This desymmetrization cannot be attributed to crystal-packing effects since it is also apparent in a structural model of 1 calculated by using DFT theory at the PBE0/LANL2DZdp level [10

Synthesis of mesomeric betaine compounds with imidazolium-enolate structure

• Nina Gonsior,
• Fabian Mohr and
• Helmut Ritter

Beilstein J. Org. Chem. 2012, 8, 390–397, doi:10.3762/bjoc.8.42

• in the space group P21/c (No. 14). The bond distances of O(3)–C and O(1)–C were 1.241(4) Å and 1.228(4) Å, respectively. These correspond to the values of the C=O double bonds. In the crystal packing, molecule layers were formed due to very weak π–π stacking of the aromatic rings (Figure 4

• bending, imidazole), 842, 748. 1H NMR spectrum of mesomeric betaine 3. 13C NMR spectrum of dipole 3. Solid-state molecular structure of compound 3. Selected bond distances [Å]: O(1)–C 1.228(4), O(2)–C 1.204(4), O(3)–C 1.241(4). Formation of molecular layers in the crystal packing. Higuchi–Connors phase

Double N-arylation reaction of polyhalogenated 4,4’-bipyridines. Expedious synthesis of functionalized 2,7-diazacarbazoles

• Mohamed Abboud,
• Emmanuel Aubert and
• Victor Mamane

Beilstein J. Org. Chem. 2012, 8, 253–258, doi:10.3762/bjoc.8.26

• diffraction and show π–π stacking involving the diazacarbazole moieties and the phenyl rings of functionalized groups. Keywords: 4,4’-bipyridine; cross-coupling; crystal packing; diazacarbazole; X-ray diffraction; Introduction Only a few examples of the preparation of diazacarbazoles have been reported [1

• (dihedral angles of 50.90(4)° for 3b, 59.00(6)° and 48.45(5)° for 12c). On the opposite, the methylsulfanylphenyl groups in 12c are almost coplanar with the diazacarbazole moiety (dihedral angles of 2.17(15)°/13.92(11)° and 8.30(14)°/13.86(11)°). In both compounds the crystal packing is governed by π–π