Crystal Engineering with Symmetrical Threefold Acceptor-Substituted Triaminobenzenes

Wolff, Jens; Gredel, Frank; Oeser, Thomas; Irngartinger, Hermann; Pritzkow, Hans

doi:10.1002/(sici)1521-3765(19990104)5:1<29::aid-chem29>3.0.co;2-5

Cited by 44 publications

(38 citation statements)

References 26 publications

(31 reference statements)

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“…Moreover, although X-ray structural and computational investigations of hydrogen-bonding systems date back several decades (Leiserowitz, 1976;Del Bene & Kochenour, 1976), considerable effort is currently focused (Coupar et al, 1997;Ferguson et al, 1997;Sùrensen & Larsen, 2003) on understanding crystal-packing interactions (particularly hydrogen bonds) at a level that may one day underpin the development of calculation methods that accurately predict crystal structures for small molecules. Lastly, the formation of hydrogen bonds in several types of nitro compound has attracted considerable theoretical and experimental interest (Szczesna & Urbanczyk-Lipkowska, 2002;Chen & Tzeng, 1999;Hanuza et al, 1998) due mainly to the ubiquity of organic nitro derivatives, their use as explosives (Bemm & Ostmark, 1998) and the generally strong hydrogenbond acceptor character of nitro group O atoms (Wolff et al, 1999;Yan & Zhu, 1999;Rablen et al, 1998).…”

Section: Introductionmentioning

confidence: 99%

Conformational analysis: crystallographic, molecular mechanics and quantum chemical studies of C—H...O hydrogen bonding in the flexible bis(nosylate) derivative of catechol

Munro

Mariah

2004

Acta Crystallogr Sect B

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The single-crystal X-ray diffraction analysis of 2-[[(4-nitrophenoxy)sulfonyl]oxy]phenyl 4-nitrophenyl sulfate (4) reveals that an interesting intermolecular or extended structure (a one-dimensional hydrogen-bonded polymer) is formed because of pairs of intermolecular (aryl)C--H...O(nitro) hydrogen bonds between the C(2) symmetry monomer units. The axis of the hydrogen-bonded polymer runs co-linear with the [101] face diagonal of the monoclinic unit cell. Molecular mechanics calculations using a modified version of the MM+ force field and a random conformational search algorithm have been used to locate the important low-energy in vacuo conformations of (4). The MM-calculated conformation of (4) that most closely matches the X-ray structure lies some 26.5 kJ mol(-1) higher in energy than the global minimum-energy conformation, consistent with the notion that the crystallographically observed molecular architecture of (4) is a local energy minimum in the absence of its crystal lattice environment. Since the X-ray conformation of (4) was correctly calculated only when all of the neighbouring molecules in the crystal lattice were included in the simulation, hydrogen bonding and other non-bonded interactions in the crystal lattice clearly dictate the experimentally observed conformation of (4). Quantum chemical calculations (AM1 method) confirm the critical role played by the intermolecular (aryl)C--H...O(nitro) hydrogen bonds in controlling the crystallographically observed conformation of (4) and show that self-recognition in this system by hydrogen bonding is favoured on electrostatic grounds. Collectively, the molecular simulations suggest that because the lowest-energy molecular conformation of (4) does not permit the formation of an extended hydrogen-bonded 'supramolecular' structure, it is not the preferred conformation in the crystalline solid state.

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Section: Introductionmentioning

confidence: 99%

Conformational analysis: crystallographic, molecular mechanics and quantum chemical studies of C—H...O hydrogen bonding in the flexible bis(nosylate) derivative of catechol

Munro

Mariah

2004

Acta Crystallogr Sect B

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“…[7] These latter segregation effects can be investigated in the frame of molecular conductors as a tool for controlling the solid state organization of open-shell molecules, a prerequisite for controlling their electronic properties in the crystalline state. In that respect, the fluorinated bis(2,2-difluoropropylenedithio)tetrathiafulvalene [8] (1) as well as the corresponding nickel dithiolene complex, [9] the bis(2,2-difluoropropylenedithioethylendithiolate)nickelate, [Ni(F 2 pdt) 2 ] ±.…”

Section: Introductionmentioning

confidence: 99%

Fluorine Segregation Controls the Solid-State Organization and Electronic Properties of Ni and Au Dithiolene Complexes: Stabilization of a Conducting Single-Component Gold Dithiolene Complex

Dautel¹,

Fourmigué²,

Canadell³

et al. 2002

Adv. Funct. Mater.

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Electrooxidation of the nickel dithiolene complex [Ni(F2pdt)2]–· (F2pdt2‐: 6,6‐difluoro‐6,7‐dihydro‐5H‐[1,4]dithiepine‐2,3‐dithiolato) affords the corresponding neutral complex [Ni(F2pdt)2]0 whose layered structure is highly reminiscent, albeit not isostructural, of that of the isosteric fluorinated bis(propylenedithio)tetrathiafulvalene and characterized by a segregation of the fluorinated moieties into fluorous bilayers. The gold neutral complex [Au(F2pdt)2]·, which is isostructural with the fluorinated bis(propylenedithio)tetrathiafulvalene, was prepared by electrocrystallization of the [n‐Bu4N][Au(F2pdt)2] salt. [Au(F2‐pdt)2]· is a semiconductor with high room temperature conductivity. The origin of this semiconducting behavior as well as possible guidelines in order to realize metallic conductivity in gold dithiolene neutral molecular solids are discussed.

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“…Ever since the work of Kitaigorodskii, it has been well-known that save for the centre of inversion, molecular symmetry need not be carried over into the crystal. 1 In the octupolar context, trigonal symmetry is particularly relevant 2,3 and whilst several trigonal molecules adopt trigonal and hexagonal crystal symmetries (or pseudosymmetric variants of these), there are many others which do not. Some combination of substituent size and awkwardness of molecular shape seems to be required for a C 3 -sym-metry molecule to adopt trigonal or quasi-trigonal crystal symmetry.…”

Section: Introductionmentioning

confidence: 99%

Shape and Size Effects in the Crystal Structures of Complexes of 1,3,5-Trinitrobenzene with some Trigonal Donors: The Benzene–Thiophene Exchange Rule

et al. 2000

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ÐThe crystal chemistry of molecular complexes of several trigonal donor molecules with the trigonal acceptor 1,3,5trinitrobenzene, TNB, is reported. Generally, replacement of a moiety by another of similar shape and size does not change the overall packing. The 1:1:1 (triphenylisocyanurate)´(TNB)´(benzene) solvate is isostructural to the corresponding 1:1:1 thiophene solvate, con®rming the so-called benzene±thiophene exchange rule. The 1:1 complex of tris-2,4,6-(4-methylphenyl)-1,3,5-triazine and TNB is layered and the layers have quasi-trigonal symmetry. The triazine ring may be replaced by a phenyl ring without any change in the crystal structure. Thus, 1,3,5-tris(4-methylphenyl)benzene and TNB form an isostructural 1:1 complex. Such shape/ size exchange may be further explored in the 1:1 complex of 1,3,5-tris[5-(2-chlorothienyl)]benzene and TNB. Here both phenyl± thienyl and chloro±methyl exchanges are simultaneously possible and yet another isostructural complex is obtained. Finally, the 1:1 complex of 1,3,5-tris(2-thienyl)benzene and TNB is also found to have a very similar structure. However, when 1,3,5-triphenylbenzene and TNB are taken in 1:1 ratio in solution, the result is a 1:3 molecular complex. This is unexpected in view of the phenyl±thienyl exchange rule, and some rationalisation is provided for the unusual formation of this 1:3 complex. Many of these structures are pertinent from the viewpoint of carry-over of trigonal molecular symmetry into the crystal, a contemporary theme in the engineering of crystal structures for octupolar non-linear optical applications, while ready access to the 1,3,5-trisubstituted benzenes for this study was made possible by a general and ef®cient protocol for the synthesis of these compounds from the corresponding acetyl aromatics.

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Crystal Engineering with Symmetrical Threefold Acceptor-Substituted Triaminobenzenes

Cited by 44 publications

References 26 publications

Conformational analysis: crystallographic, molecular mechanics and quantum chemical studies of C—H...O hydrogen bonding in the flexible bis(nosylate) derivative of catechol

Conformational analysis: crystallographic, molecular mechanics and quantum chemical studies of C—H...O hydrogen bonding in the flexible bis(nosylate) derivative of catechol

Fluorine Segregation Controls the Solid-State Organization and Electronic Properties of Ni and Au Dithiolene Complexes: Stabilization of a Conducting Single-Component Gold Dithiolene Complex

Shape and Size Effects in the Crystal Structures of Complexes of 1,3,5-Trinitrobenzene with some Trigonal Donors: The Benzene–Thiophene Exchange Rule

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