“Conformational lock” via unusual intramolecular C–F⋯OC and C–H⋯Cl–C parallel dipoles observed in in situ cryocrystallized liquids

Dey, Dhananjay; Bhandary, Subhrajyoti; Sirohiwal, Abhishek; Hathwar, Venkatesha R.; Chopra, Deepak

doi:10.1039/c6cc02535h

Cited by 32 publications

(41 citation statements)

References 26 publications

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“…For the sake of comparison, the energetics of 4FBC 20 and 23DFBC 20,51 were also taken into account along with this current study. In our previous report, 51 we have described only the molecular conformation of BC, 2FBC, 23DFBC, 24DFBC, 25DFBC and 26DFBC stabilized by the presence of ''only'' intramolecular interactions of the type C-HÁ Á ÁCl-C, C-FÁ Á ÁOQC and C-FÁ Á ÁCl-C. In the current study, we have discussed the role of weak intermolecular interactions that play a crucial role towards the stabilization of the overall crystal packing, in the absence of any strong interaction via the analysis of the energy frameworks.…”

Section: Resultsmentioning

confidence: 99%

Energy frameworks and a topological analysis of the supramolecular features in in situ cryocrystallized liquids: tuning the weak interaction landscape via fluorination

Dey

Bhandary

Thomas

et al. 2016

Phys. Chem. Chem. Phys.

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Weak intermolecular interactions observed in crystalline materials are often influenced or forced by stronger interactions such as classical hydrogen bonds. Room temperature liquids offer a scenario where such strong interactions are absent so that the role and nature of the weak interactions can be studied more reliably. In this context, we have analyzed the common organic reagent benzoyl chloride (BC) and a series of its fluorinated derivatives using in situ cryocrystallography. The intermolecular interaction energies have been estimated and their topologies explored using energy framework analysis in a series of ten benzoyl chloride analogues, which reveal that the ππ stacking interactions serve as the primary building blocks in these crystal structures. The crystal packing is also stabilized by a variety of interaction motifs involving weak C-HO/F/Cl hydrogen bonds and FF, FCl, and ClCl interactions. It is found that fluorination alters the electrostatic nature of the benzoyl chlorides, with subsequent changes in the formation of different weak interaction motifs. The effects of fluorination on these weak intermolecular interactions have been systematically analyzed further via detailed inputs from a topological analysis of the electron density and Hirshfeld surface analysis.

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Section: Resultsmentioning

confidence: 99%

Energy frameworks and a topological analysis of the supramolecular features in in situ cryocrystallized liquids: tuning the weak interaction landscape via fluorination

Dey

Bhandary

Thomas

et al. 2016

Phys. Chem. Chem. Phys.

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“…On obtaining quality crystals of the in situ cryocrystallized organometallic liquids, these were checked for their single‐crystal behavior. The crystallization process is similar to the procedure followed in our previous study . Figure depicts the still images for the corresponding crystals of complex I and II at 110(2) K. The detailed experimental set up, crystallization procedure, crystallographic data obtained after spherical atom refinement, and other details are shown in the Supporting Information (Table S1–S2).…”

Section: Methodsmentioning

confidence: 96%

Investigation of Chemical Bonding in In Situ Cryocrystallized Organometallic Liquids

et al. 2017

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This Communication presents the crystal structure of the organometallic complexes (η -1,3-cyclohexadiene) iron tricarbonyl (I) and (methyl cyclopentadienyl) manganese tricarbonyl (II) which are both liquid at room temperature. The crystal structures were determined using a state-of-the-art in situ cryocrystallization technique. The bonding features were elucidated using topological analysis of charge density in the framework of quantum theory of atoms in molecules (QTAIM) and theoretical charge density analysis (multipolar refinement), to decipher the metal-carbonyl, metal-olefin and metal-carbocyclic ligand interactions in these complexes. Complex I displayed a simultaneous interplay of a "synergic effect" (σ-donation and π-back-bonding in the metal and an end-on coordinated carbonyl interaction) as well as consistency with the Dewar-Chatt-Duncanson (DCD) model (metal and side-on coordinated π-ligand interactions).

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“…Their investigation reveals that the participation of organofluorine [C(any)-F] was found to be 0.2% (out of 2885 occurrences; CSD) and 1.3% (out of 1856 occurrences; PDB), whereas the value for fluorine attached to the Csp 3 atom was found to be 0.3% (out of 2095 occurrences; CSD) and 0.2% (out of 553 occurrences; PDB). In our recent study (Dey et al, 2016) of in situ cryo-crystallized 2-fluorobenzoyl chloride, we have established the importance of intramolecular FÁ Á ÁO contacts in facilitating a conformational lock in the molecule.…”

Section: Introductionmentioning

confidence: 95%

Characterization of fluorine-centred `F...O' σ-hole interactions in the solid state

Sirohiwal

Hathwar

Dey

et al. 2017

Acta Crystallogr B Struct Sci Cryst Eng Mater

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In the current study, the crystal structure of 1-(3-nitrophenyl)-2,2,2-trifluoroethanone (A1) and (E)-4-((4-fluorophenyl) diazenyl)phenol (A2) has been analyzed for the characterization of the presence of a `unique' and `rare' intermolecular C(sp/sp)-F...O contact, which has been observed to play a significant role in the crystal packing. Theoretical charge-density calculations have been performed to study the nature and strength associated with the existence of this intermolecular F...O contact, wherein the F atom is attached to an sp-hybridized C atom in the case of A1 and to an sp hybridized carbon in the case of A2. The crystal packing of the former contains two `electronically different' Csp-F...O contacts which are present across and in between the layers of molecules. In the latter case, it is characterized by the presence of a very `short' (2.708 Å) and `highly directional' (168° at ∠C4-F1...O1 and 174° at ∠C10-O1...F1) Csp-F...O contact. According to the Cambridge Structural Database (CSD) study, it is a rare example in molecular crystals. Topological features of F...O contacts in the solid state were compared with the gas-phase models. The two-dimensional and three-dimensional static deformation density obtained from theoretical multipole modeling confirm the presence of a charge depleted region on the F atoms. Minimization of the electrostatic repulsion between like charges are observed through subtle arrangements in the electronic environment in two of the short intermolecular F...O contacts. These contacts were investigated using inputs from pair energy decomposition analysis, Bader's quantum theory of atoms in molecules (QTAIM), Hirshfeld surface analysis, delocalization index, reduced density gradient (RDG) plot, electrostatic potential surface and distributed atomic polarizability. The intermolecular energy decomposition (PIXEL) and RDG-NCI (non-covalent interaction) analysis of the F...O contacts establish the interaction to be dispersive in nature. The mutual polarization of an O atom by fluorine and vice versa provides real physical insights into the role of atomic polarizability in interacting atoms in molecules in crystals.

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“Conformational lock” via unusual intramolecular C–F⋯OC and C–H⋯Cl–C parallel dipoles observed in in situ cryocrystallized liquids

Cited by 32 publications

References 26 publications

Energy frameworks and a topological analysis of the supramolecular features in in situ cryocrystallized liquids: tuning the weak interaction landscape via fluorination

Energy frameworks and a topological analysis of the supramolecular features in in situ cryocrystallized liquids: tuning the weak interaction landscape via fluorination

Investigation of Chemical Bonding in In Situ Cryocrystallized Organometallic Liquids

Characterization of fluorine-centred `F...O' σ-hole interactions in the solid state

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