Hydrogen-Bonded Ribbons, Tapes and Sheets as Motifs for Crystal Engineering

Meléndez, Rosa E.; Hamilton, Andrew D.

doi:10.1007/3-540-69178-2_3

Cited by 114 publications

(51 citation statements)

References 71 publications

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“…The main structural features of interest are the O-O′ intermolecular hydrogen bonding distance and the difference in the C 23 and C 12 bond lengths. This latter quantity is the difference in bond length between the nominal single bond and the nominal double bond in the conjugated system.…”

Section: Discussionmentioning

confidence: 99%

The Crystalline Enol of 1,3-Cyclohexanedione and Its Complex with Benzene: Vibrational Spectra, Simulation of Structure and Dynamics and Evidence for Cooperative Hydrogen Bonding

et al. 2004

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The inelastic incoherent neutron scattering spectra of 1,3-cyclohexanedione (CHD) in its crystalline enol form and its cyclamer complexes with benzene and benzene-d 6 are compared with each other, with IR and Raman spectra and with the results of calculations using density functional theory (DFT). The crystal packing of the CHD enol is a linear hydrogen-bonded chain with conjugated donor and acceptor groups analogous to that found in peptide hydrogen bonding. The benzene complex is a closed hexameric hydrogen-bonded cycle. A DFT treatment is applied to the full hexamer of the benzene complex. The CHD chain is treated as a series of finite linear clusters by DFT, while the infinite one-dimensional chain and the three-dimensional crystal are treated by periodic DFT. Comparison is made with both the observed crystal structures and the vibrational spectra. The very good to excellent agreement of the computed vibrational spectra with experiment demonstrates that the models and computational treatments used are reliable. The theoretical treatment of the linear chain clusters exhibits a continuous change in structure with increasing chain length, converging to values near the observed structure. Emphasis is placed on the cooperative nature of hydrogen bonding in CHD as revealed by these systematic trends. The ability of DFT methods to treat hydrogen bonding in solids appears to be roughly as accurate as the crystal structure determinations.1,3-Cyclohexanedione (CHD) exists in its enol form in the solid state where it forms hydrogen-bonded chains with an antianti configuration having short (2.56 Å) O-O hydrogen bonding distances. 1 This structure is of interest for several reasons including the ordered hydrogen bonding arrangement, an orderdisorderphasetransitionthatinvolveshydrogenbondinterchange, 2-6 and indications derived from examination of crystal structures that CHD is an example of a resonance-assisted, cooperative hydrogen bonding network. [7][8][9][10][11][12][13] This cooperativity arises from the fact that when the enol of CHD forms a hydrogen bond, this polarizes the molecule such that the formation of an additional hydrogen bond with another CHD is more favorable. This may be thought of as due to an enhanced contribution of the ionic resonance form. When crystallized from benzene, this material forms a unique cyclamer structure (CHD 6 Bz) in which six CHD molecules form a syn-anti hydrogen bonded ring surrounding a central benzene molecule. 14 The related 1,3-cyclopentanedione (CPD) 15 forms an antianti linear chain structure very much like that of CHD. Methyl substitution of CPD or CHD can result in changes to the hydrogen-bonding pattern. 2-Methyl-CPD forms a linear chain with an anti-syn arrangement. 16 In this case the methyl-CHD molecules in a given linear chain all point in the same direction. This is in contrast to the anti-anti chain of CPD and CHD (Figure 1) where alternate molecules are oriented in opposite directions. The 2-methyl derivative of CHD has a structure similar to that of CHD 17 but t...

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Section: Discussionmentioning

confidence: 99%

The Crystalline Enol of 1,3-Cyclohexanedione and Its Complex with Benzene: Vibrational Spectra, Simulation of Structure and Dynamics and Evidence for Cooperative Hydrogen Bonding

et al. 2004

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“…It is clear that assembly of the molecules via carboxylic pairing (9,26) would result in a highly expanded and thus presumably too labile structure (27,28). As a possible consequence of this, we did not succeed to grow a crystal of 1 in its solvent free state.…”

Section: X-ray Structural Studymentioning

confidence: 99%

Unusual mixed solvent supramolecular crystal framework formed of a new tecton-like tetracarboxylic building block

Hauptvogel

Seichter

Weber

2011

Supramolecular Chemistry

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“…[1][2][3] There remains a need to develop new "supramolecular synthons" that can be used to create supramolecular structures with novel three-dimensional architectures. We now report a new molecular recognition motif, the bicyclic N, N′-diacylaminal ("amidal").…”

mentioning

confidence: 99%

“…Infinite tapes sustained by R 2 2 (8)-type hydrogen bonds are common, but those in which the hydrogen-bonded units are not coplanar are rare. 1,2,14 The manner in which the tapes and the solvent pack differs dramatically among the three crystals (see the Supporting Information).…”

mentioning

confidence: 99%

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The Bicyclic N,N‘-Diacylaminal: A New Motif for Molecular Self-Assembly

Grossman¹,

Hattori²,

Parkin³

et al. 2002

J. Am. Chem. Soc.

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W This paper contains enhanced objects available on the Internet at http://pubs.acs.org/journals/jacsat.The principles governing noncovalent self-assembly have been studied intensely recently because of their potential relevance to nanotechnology. [1][2][3] There remains a need to develop new "supramolecular synthons" that can be used to create supramolecular structures with novel three-dimensional architectures. We now report a new molecular recognition motif, the bicyclic N, N′-diacylaminal ("amidal"). In the solid state, the amidals described here self-assemble into either "supramolecular chair cyclohexanes" occupied by two aromatic solvent molecules or infinite tapes. The amide dimers sustaining these supramolecular structures are not coplanar, making these structures uniquely three-dimensional.We have recently reported tricyclic amidals 1 and 2 (eq 1). 4 Amidal 1 crystallizes from toluene, chlorobenzene, and benzotrifluoride in the triclinic space group P1 in the stoichiometry (1) 3 ‚ (solvent) (mps 197-199°C). Only minor differences (mostly involving the CO 2 Et groups) distinguish the three types of 1 within each crystal, and the three (1) 3 sets of the three crystals are nearly superimposable. In each crystal, six amidals (each independent molecule and its enantiomer) self-assemble into a squat cylindrical hexamer occupied by two aromatic guests (Figures 1 and 2). Each monomer makes two hydrogen bonds to each of its neighbors, and the vertical orientation of the amidals alternates around the hexamer, endowing the hexamer with approximate D 3d and exact C i symmetry. The cavities of the hexamers are lined at the top and bottom by the CH 2 CH 2 groups of 1 and in the middle by the CONH groups. The hexamers stack to form six-sided straws occupied by aromatic solvent. These straws are close-packed into roughly hexagonal arrays, like bundles of pencils. The approximate D 3d symmetry of the hexamers allows them to be regarded as supramolecular analogues of chair-shaped cyclohexane. The only previously reported "supramolecular chair" is sustained by C-H‚‚‚π interactions and lacks an occupant. 5 By contrast, our chairs are sustained by more robust amide dimers, and, in each chair, two arenes sit locked in intimate embrace. The volumes of the interiors of the cylinders in the three crystals, computed by subtracting the atomic volumes of the atoms making up the cylinders from the volume of the unit cell, 6 are approximately 340, 330, and 342 Å 3 , respectively, at room temperature. (Each contracts by 11 Å 3 at 90 K.) Each pair of guests is calculated to occupy 282, 272, and 319 Å 3 , respectively, at room temperature. Only in (1) 6 (C 6 H 5 CF 3 ) 2 is the volume of the cylinder occupied fully by the guests; in the others, the excess space is evident from the increased thermal motion of the guests.In (1) 6 (C 7 H 8 ) 2 , the two guests are arranged in a face-to-face and CH 3 -to-center orientation, whereas in (1) 6 (C 6 H 5 Cl) 2 and (1) 6 (C 6 H 5 -CF 3 ) 2 , they are arranged in a face-to-face and edge-to-edge o...

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Hydrogen-Bonded Ribbons, Tapes and Sheets as Motifs for Crystal Engineering

Cited by 114 publications

References 71 publications

The Crystalline Enol of 1,3-Cyclohexanedione and Its Complex with Benzene: Vibrational Spectra, Simulation of Structure and Dynamics and Evidence for Cooperative Hydrogen Bonding

The Crystalline Enol of 1,3-Cyclohexanedione and Its Complex with Benzene: Vibrational Spectra, Simulation of Structure and Dynamics and Evidence for Cooperative Hydrogen Bonding

Unusual mixed solvent supramolecular crystal framework formed of a new tecton-like tetracarboxylic building block

The Bicyclic N,N‘-Diacylaminal: A New Motif for Molecular Self-Assembly

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