CH/<i>π</i> Interaction in the Crystal Structure of Organic Compounds. A Database Study

Umezawa, Yōji; Tsuboyama, Sei; Honda, Kazumasa; Uzawa, Jun; Nishio, Motohiro

doi:10.1246/bcsj.71.1207

Cited by 395 publications

(192 citation statements)

References 60 publications

Supporting

Mentioning

176

Contrasting

Order By: Relevance

“…[1][2][3] In spite of their weakness, non-classical hydrogen bonds have been frequently invoked in systems from macromolecules to biomolecules to explain physical and chemical properties such as crystal structures, conformations, and reactivity. 1,2,4 The detailed nature of such interactions remains insufficiently understood, and may include aspects such as charge transfer contributions from the π system to C-H antibonding orbitals, as well as London dispersion. [5][6][7][8] Deeper understanding will benefit from quantitative characterization of systems such as the bimolecular complexes presented here.…”

Section: Introductionmentioning

confidence: 99%

“…9. Among these are van der Waals complexes M·S of aromatic chromophores M such as benzene, 10 paradifluorobenzene, 11,12 phenol, 13 anisole, 14 indole, 15 dibenzop-dioxin, 16 and carbazole [17][18][19] with noble gases (S = Ne, Ar, Kr, Xe), or small closed-shell molecules (S = N 2 , CO, CH 4 ). 19 In these cases, linear correlation of D 0 (S 0 ) with the polarizability of the S atom or molecule was observed, as expected from London dispersion theory.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Accurate dissociation energies of two isomers of the 1-naphthol⋅cyclopropane complex

Maity

Knochenmuss

Holzer

et al. 2016

The Journal of Chemical Physics

View full text Add to dashboard Cite

Articles you may be interested inInfluences of the propyl group on the van der Waals structures of 4-propylaniline complexes with one and two argon atoms studied by electronic and cationic spectroscopy J. Chem. Phys. 143, 034308 (2015); 10.1063/1.4927004The weak hydrogen bond in the fluorobenzene-ammonia van der Waals complex: Insights into the effects of electron withdrawing substituents on π versus in-plane bonding J. Chem. Phys. 126, 154319 (2007) The 1-naphthol·cyclopropane intermolecular complex is formed in a supersonic jet and investigated by resonant two-photon ionization (R2PI) spectroscopy, UV holeburning, and stimulated emission pumping (SEP)-R2PI spectroscopy. Two very different structure types are inferred from the vibronic spectra and calculations. In the "edge" isomer, the OH group of 1-naphthol is directed towards a C-C bond of cyclopropane, the two ring planes are perpendicular. In the "face" isomer, the cyclopropane is adsorbed on one of the π-aromatic faces of the 1-naphthol moiety, the ring planes are nearly parallel. Accurate ground-state intermolecular dissociation energies D 0 were measured with the SEP-R2PI technique. The D 0 (S 0 ) of the edge isomer is bracketed as 15.35 ± 0.03 kJ/mol, while that of the face isomer is 16.96 ± 0.12 kJ/mol. The corresponding excited-state dissociation energies D 0 (S 1 ) were evaluated using the respective electronic spectral shifts. Despite the D 0 (S 0 ) difference of 1.6 kJ/mol, both isomers are observed in the jet in similar concentrations, so they must be separated by substantial potential energy barriers. Intermolecular binding energies, D e , and dissociation energies, D 0 , calculated with correlated wave function methods and two dispersion-corrected density-functional methods are evaluated in the context of these results. The density functional calculations suggest that the face isomer is bound solely by dispersion interactions. Binding of the edge isomer is also dominated by dispersion, which makes up two thirds of the total binding energy. Published by AIP Publishing. [http://dx

show abstract

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Accurate dissociation energies of two isomers of the 1-naphthol⋅cyclopropane complex

Maity

Knochenmuss

Holzer

et al. 2016

The Journal of Chemical Physics

View full text Add to dashboard Cite

show abstract

“…3). Although the intramolecular multiple (C)H· · ·C contacts of about 3.3 Å are longer than those (up to 3.2 Å) described by Nishio et al, 23) they could prevent free rotation of the bulky trityl and tert-butyl substituents. It is worth noting that the recent detailed calculations of intermol- (1) 3443 (5) Ϫ1870 (3) 1600 (2) 45 (1) C (3) 4246 (6) Ϫ1513 (3) 2143 (2) 46 (1) O (2) 3694 (4) Ϫ1449 (3) 2619 (2) 64 (1) O (1) 5631 (4) Ϫ1278 (2) 1993 (2) 51 (1) C (4) 6635 (6) Ϫ785 (4) 2404 (3) 59 (2) C (41) 6953 (7) Ϫ1345 (4) 2943 (3) 74 (2) C (42) 8028 (7) Ϫ668 (5) 2032 (3) 93 (2) C (43) 5944 (8) 117 (4) 2553 (3) 81 (2) N (1) 2045 (5) Ϫ2251 (3) 1777 (2) 50 (1) C (5) 1308 (6) Ϫ2822 (4) 1417 (3) 57 (1) O (4) 1804 (5) Ϫ3146 (3) 976 (2) 93 (2) …”

Section: Resultsmentioning

confidence: 62%

The Molecular and Crystal Structure of tert-Butyl N.ALPHA.-tert-Butoxycarbonyl-L-(S-trityl)cysteinate and the Conformation-Stabilizing Function of Weak Intermolecular Bonding.

Kozioł

Szady

Masiukiewicz

et al. 2001

CHEMICAL & PHARMACEUTICAL BULLETIN

View full text Add to dashboard Cite

The title compound, C 31 H 37 NO 4 S {systematic name: (R)-tert-butyl-2-[(tert-butoxycarbonyl)amino]-3-(tritylsulfanyl)propanoate} is an L-cysteine derivative with three functions: NH 2 , COOH and SH, blocked by protecting groups tert-butoxycarbonyl, tert-butyl and trityl, respectively. The main chain of the molecule adopts the extended, nearly all-trans C 5 conformation with the intramolecular N-H· · · O‫؍‬C hydrogen bond. The urethane group is not involved in any intermolecular hydrogen bonding. Only weak intermolecular hydrogen bonds and hydrophobic contacts are observed in the crystal structure. These are C-H· · ·O hydrogen bonds and CH/p p interactions with donor· · ·acceptor distances, C· · ·O ca. 3.5 Å and C· · ·C ca. 3.7 Å, respectively. The first type of interaction links phenyl H-atoms and carbonyl groups. The second type of interaction is formed between a methyl group of the tert-butyl fragment and a trityl phenyl ring. The resulting molecular conformation in the crystal is very close to an ab initio minimum energy conformer of the isolated molecule. The extended C 5 conformation of the main peptide chain is the same and there is slight discrepancy in the disposition of trityl phenyl rings. Their small dislocation creates the possibility of forming the entire network above of extensive, specific, weak intermolecular interactions; these constrain the molecule and permit it to retain the minimum energy C 5 conformation of its main chain in the solid state. In contrast, in n-hexane solution, where such specific interactions cannot occur, only a small population of the molecules adopts the extended C 5 conformation.

show abstract

“…This arrangement is frequently observed for the self association of 3-carboxycoumarins. 13 The A-A´ π-assembly formed ( Figure 3a), is also associated through C6⎯H···Ph interactions 19 ( Table 1). The angle between the phenethyl and coumarin ring mean planes is close to 93º providing the length and flexibility required for this interaction to occur.…”

mentioning

confidence: 99%

“…The acceptors 2a and 2b, bearing a pendant phenethyl or benzyl group, are self associated through T-shaped interactions 19 or through Ph-Ph π-stacking interactions, respectively, thereby favoring the alternated D-A-A'-D' π-stacking pattern observed in complexes 3 and 4. In contrast, the alternated D-A π-stacking pattern is exhibited by complex 5, in which the possibility intermolecular H-bonding of 2c is missing.…”

mentioning

confidence: 99%

Supramolecular assembly of 2-aminobenzothiazole and N-[(2-oxo-2H-1-benzopyran-3-yl)carboxyl]phenethylamide donor-acceptor complex. A comparative study

Garcı́a-Báez¹,

Martínez‐Martínez²,

Höpfl³

et al. 2003

Arkivoc

View full text Add to dashboard Cite

In this paper the synthesis and solid state characterization of the donor-acceptor (D-A) complex between 2-aminobenzothiazole (ABT) and N- [(2-oxo-2H-1-benzopyran-3-yl)carboxyl]phenethylamide is reported. A comparison is performed with other aminobenzothiazole-coumarin complexes reported earlier and the results are analyzed in the context of crystal engineering. A common feature of these structures is the presence of a building block formed by pair-wise self complementary NH···N interactions between two molecules of ABT, defining an R 2 2 (8) motif. The complete three-dimensional supramolecular arrangement is achieved by both strong (NH···O) and weak (CH···X, X = O, aryl) H-bonding interactions which define an A···D···D'···A' hydrogen bonded tetrameric unit, which packs through π-stacking interactions. The resulting donor-acceptor assemblies present two patterns of alternated stacking: D-A and D-A-A'-D'. Finally, the factors ruling the supramolecular isomerism exhibited by these complexes and the nature of the interactions are discussed and supported by ab initio theoretical calculations.

show abstract

CH/π Interaction in the Crystal Structure of Organic Compounds. A Database Study

Cited by 395 publications

References 60 publications

Accurate dissociation energies of two isomers of the 1-naphthol⋅cyclopropane complex

Accurate dissociation energies of two isomers of the 1-naphthol⋅cyclopropane complex

The Molecular and Crystal Structure of tert-Butyl N.ALPHA.-tert-Butoxycarbonyl-L-(S-trityl)cysteinate and the Conformation-Stabilizing Function of Weak Intermolecular Bonding.

Supramolecular assembly of 2-aminobenzothiazole and N-[(2-oxo-2H-1-benzopyran-3-yl)carboxyl]phenethylamide donor-acceptor complex. A comparative study

Contact Info

Product

Resources

About