Structural studies of N-(2′-substituted phenyl)-9,10-dihydro-9,10-ethanoanthracene-11,12-dicarboximides by X-ray diffraction and NMR spectroscopy—proofs for CH/π interactions in liquid and solid phases

Großmann, G.; Potrzebowski, Marek J.; Olejniczak, Sebastian; Ziółkowska, Natasza E.; Bujacz, G.; Ciesielski, W.; Prezdo, Wiktor; Nazarov, V. B.; Golovko, Vladislav

doi:10.1039/b300759f

Cited by 19 publications

(20 citation statements)

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“…Even the C-HÁ Á ÁF contacts are comparable [C5-H5Á Á ÁF2 = 2.56 Å in (IIa) and C4-H4Á Á ÁF3 = 2.51 Å in (IIb), both along (Àx + 1, Ày + 1, Àz + 1)]. Similar structures with related cell parameters were also reported by Kishikawa et al (1997), Grossmann et al (2003) and Goh & White (2009).…”

Section: Commentsupporting

confidence: 79%

“…Moreover, anthracene-2,6dicarboxylate derivatives modified with maleimides have been used in poly(ethylene terephthalate) copolymers (Jones et al, 1999). Investigations of the conformational environment of the selected derivatives were described by Csö regh et al (2003), while Grossmann et al (2003) reported NMR spectroscopic analysis of the geometric features of the orthosubstituted molecules. Verma and co-workers reported several detailed studies on the analysis of the rotation around the C aryl -N bond in, for example, o-OMe-, o-Me-, o-Cl-and o-Brsubstituted N-arylimides with dynamic and temperature-dependent NMR spectroscopy (Verma & Singh, 1976, 1978Srivastava et al, 1991).…”

Section: Commentmentioning

confidence: 99%

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Three new fluorinatedN-phenyl-substituted pentacyclic ethanoanthracenedicarboximides

Schwarzer

Weber

2011

Acta Crystallogr C

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Diels-Alder reaction between maleimides featuring 3,5-di-, 2,4,6-tri- and pentafluorinated N-phenyl substituents and anthracene yields the corresponding pentacyclic ethanoanthracenedicarboximide compounds, namely N-(3,5-difluorophenyl)-9,10-dihydro-9,10-ethanoanthracene-11,12-dicarboximide, C(24)H(15)F(2)NO(2), (IIa), N-(2,4,6-trifluorophenyl)-9,10-dihydro-9,10-ethanoanthracene-11,12-dicarboximide, C(24)H(14)F(3)NO(2), (IIb), N-(2,3,4,5,6-pentafluorophenyl)-9,10-dihydro-9,10-ethanoanthracene-11,12-dicarboximide, C(24)H(12)F(5)NO(2), (IIc). The crystal structures of (IIa)-(IIc) reveal an expected molecular geometry with a `V'-shape of the anthracene-derived tricyclic moiety. The crystal packings of (IIa) and (IIb) are dominated by π-π and C-H···O/F interactions, while F···F and C-H···π contacts are absent. In contrast, (IIc) shows F···F and C-H···O/F contacts, but no π-involved contacts of relevance.

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Section: Commentsupporting

confidence: 79%

Section: Commentmentioning

confidence: 99%

Three new fluorinatedN-phenyl-substituted pentacyclic ethanoanthracenedicarboximides

Schwarzer

Weber

2011

Acta Crystallogr C

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“…1 . Previous studies by Harano et al , 15 Shimizu et al , 9 , 17 , 18 Verma et al , 19 Grossmann et al , 20 and Yamada et al 21 have demonstrated that N -arylimide molecular balances exhibit slow rotation about the C aryl –N imide bond at room temperature (Δ G ‡ ∼ 20 kcal mol –1 ). 9 , 22 The slowly rotating C aryl –N imide bond (indicated in red in Fig.…”

Section: Resultsmentioning

confidence: 96%

Quantitative model for rationalizing solvent effect in noncovalent CH–Aryl interactions

et al. 2016

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“…15 The rigid bicyclic framework fixes the position of most of the atoms, which greatly simplifies its conformational analysis. The only major degree of rotational freedom is the C−N single bond connecting the o-tolyl rotor to the succinimide ring.…”

mentioning

confidence: 99%

Correlation between Solid-State and Solution Conformational Ratios in a Series of N-(o-Tolyl)Succinimide Molecular Rotors

Hwang

Maier

et al. 2015

Crystal Growth & Design

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The syn-anti conformational equilibrium of a library of 30 N-(o-tolyl)succinimide molecular rotors was measured in solution via 1 H NMR and in the solid-state via Xray crystallography. A strong correlation was observed between the solution and solid-state mole fractions of syn-conformers (χ syn ). All rotors, even those with a small conformational preference in solution (±0.15 kcal/mol), displayed the same conformation in their crystal structures. The conformational preferences in the crystals tended to be more pronounced with a predominance of all syn-or anti-structures. However, when the rotors had no conformational preference in solution, the conformational preferences in the crystal structures varied widely. X -ray crystallography is a powerful tool in modern chemistry and biochemistry for the determination of the three-dimensional structure of natural products, 1,2 rational drug design, 3,4 and the study of noncovalent interactions 5−7 and solid-form pharmaceuticals. 8,9 An important question in these studies is whether an X-ray crystal structure accurately reflects the conformation in solution. 10−12 Conversely, can the conformation in solution be used to predict the conformation in a crystal structure? To address these questions, the X-ray crystal structure and solution conformational ratios for a series of 30 molecular rotors based on an atropisomeric bicyclic N-(otolyl)succinimide framework were measured and compared ( Figure 1).The suitability of atropisomeric N-arylsuccinimides for studying the correlation between solid-state and solution structures was previously recognized by Verma, 13 Kishikawa, 14 and Grossmann. 15 The rigid bicyclic framework fixes the position of most of the atoms, which greatly simplifies its conformational analysis. The only major degree of rotational freedom is the C−N single bond connecting the o-tolyl rotor to the succinimide ring. Due to steric repulsion between the orthomethyl group of the rotor and the imide carbonyls, the N-tolyl and succinimide rings avoid the coplanar geometry. This leads to anti-and syn-atropisomers that are conformationally distinct due to the asymmetry of the succinimide ring arising from the fused bicyclic framework.In the course of our studies using molecular balances to measure weak noncovalent interactions, 16−23 we realized that we had access to a library of 30 N-(o-tolyl)succinimide rotors that displayed a wide range of anti-/syn-conformational ratios (Figure 2). This provided a unique opportunity to examine the correlation or lack of correlation between their solid-state and solution structures. By comparison, the scope of previous studies utilizing this framework 18,20,23 was based on a small number of structures (12−14) limiting the certainty and generality of the observed trends.We specifically focused on bicyclic N-(o-tolyl)succinimides with ortho-methyl groups because their atropisomers are generally bereft of the common factors that lead to differences in solid-state and solution structures. 24,25 First, the ortho-methyl group is nonpol...

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Structural studies of N-(2′-substituted phenyl)-9,10-dihydro-9,10-ethanoanthracene-11,12-dicarboximides by X-ray diffraction and NMR spectroscopy—proofs for CH/π interactions in liquid and solid phases

Cited by 19 publications

References 20 publications

Three new fluorinatedN-phenyl-substituted pentacyclic ethanoanthracenedicarboximides

Three new fluorinatedN-phenyl-substituted pentacyclic ethanoanthracenedicarboximides

Quantitative model for rationalizing solvent effect in noncovalent CH–Aryl interactions

Correlation between Solid-State and Solution Conformational Ratios in a Series of N-(o-Tolyl)Succinimide Molecular Rotors

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