Tetrachlorophthalic anhydride (TCPA), a refinement

Uchida, Takane; Nakano, Hirofumi; Kozawa, Kozo

doi:10.1107/s0567740882010504

Cited by 3 publications

(5 citation statements)

References 3 publications

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“…To judge the role of hydrogen bonds and short-range noncovalent forces, the halogen containing crystals were studied. The most structurally related, 4,5,6,7-tetrahalogenophthalic anhydrides, − are 3D isostructural (except 4,5,6,7-tetraiodophthalic anhydride), Table , despite the lack of hydrogen bonds. Isostructural are also hexahalogenobenzenes (C 6 F 6 , C 6 Cl 6 , C 6 Br 6 , and C 6 I 6 ), − 1,2-dibromo-1,3-dibromo- and 1,4-dibromo-2,3,5,6-tetrachlorobenzene, and 1,4-dibromo-2,3,5,6-tetraiodobenzene, as well as p -halogenoethynylbenzenes ( p -chloro-, p -bromo-, and p -iodoethynylbenzene) .…”

Section: Resultsmentioning

confidence: 99%

Quantum-Chemical Insight into Structure–Reactivity Relationship in 4,5,6,7-Tetrahalogeno-1H-benzimidazoles: A Combined X-ray, DSC, DFT/QTAIM, Hirshfeld Surface-Based, and Molecular Docking Approach

Latosińska

Maurin

et al. 2014

J. Phys. Chem. A

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The weak interaction patterns in 4,5,6,7-tetrahalogeno-1H-benzimidazoles, protein kinase CK2 inhibitors, in solid state are studied by the X-ray method and quantum chemistry calculations. The crystal structures of 4,5,6,7-tetrachloro- and 4,5,6,7-tetrabromo-1H-benzimidazole are determined by X-ray diffraction and refined to a final R-factor of 3.07 and 3.03%, respectively, at room temperature. The compound 4,5,6,7-tetrabromo-1H-benzimidazole, which crystallizes in the I41/a space group, is found to be isostructural with previously studied 4,5,6,7-tetraiodo-1H-benzimidazole in contrast to 4,5,6,7-tetrachloro-1H-benzimidazole, which crystallizes as triclinic P1̅ with 4 molecules in elementary unit. For 4,5,6,7-tetrachloro-1H-benzimidazole, differential scanning calorimetry (DSC) revealed a second order glassy phase transition at Tg = 95°/106° (heating/cooling), an indication of frozen disorder. The lack of 3D isostructurality found in all 4,5,6,7-tetrahalogeno-1H-benzimidazoles is elucidated on the basis of the intra- and intermolecular interactions (hydrogen bonding, van der Waals contacts, and C-H···π interactions). The topological Bader's Quantum Theory of Atoms in Molecules (QTAIM) and Spackman's Hirshfeld surface-based approaches reveal equilibration of electrostatic matching and dispersion van der Waals interactions between molecules consistent with the crystal site-symmetry. The weakening of van der Waals forces accompanied by increasing strength of the hydrogen bond (N-H···N) result in a decrease in the crystal site-symmetry and a change in molecular packing in the crystalline state. Crystal packing motifs were investigated with the aid of Hirshfeld surface fingerprint plots. The ordering 4,5,6,7-tetraiodo > 4,5,6,7-tetrabromo > 4,5,6,7-tetrachloro > 4,5,6,7-tetrafluoro reflects not only a decrease in crystal symmetry but also increase in chemical reactivity (electronic activation), which could explain some changes in biological activity of compounds from the 4,5,6,7-tetrahalogeno-1H-benzimidazole series. The ability of formation of a given type of bonds by 4,5,6,7-tetrahalogeno-1H-benzimidazole molecules is the same in the crystal and in CK2. Analysis of the interactions in the crystal permits drawing conclusions on the character (the way) of connections between a given 4,5,6,7-tetrahalogeno-1H-benzimidazole as a ligand with CK2 protein to make a protein-ligand complex.

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Section: Resultsmentioning

confidence: 99%

Quantum-Chemical Insight into Structure–Reactivity Relationship in 4,5,6,7-Tetrahalogeno-1H-benzimidazoles: A Combined X-ray, DSC, DFT/QTAIM, Hirshfeld Surface-Based, and Molecular Docking Approach

Latosińska

Maurin

et al. 2014

J. Phys. Chem. A

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“…1 and 2. Bond lengths and bond angles in TCPA are equal (within experimental error) to the values in the neat molecular crystal [9,10]. Exceptions are the bond lengths from atoms C(7) and C(8) to 0(9), where the differences are 0.012 A and 0.017 A, respectively.…”

Section: Crystal Structurementioning

confidence: 84%

Characterization of the Phenanthrene-Tetrachlorophthalic Anhydride (P/TCPA) 1:1 Charge-Transfer Crystal: Spectroscopic and Structural Investigations

Krzystek

Schütz

Wolf

et al. 1987

Zeitschrift Für Naturforschung A

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The 1:1 phenanthrene-tetrachlorophthalic anhydride (P/TCPA) charge-transfer complex crystalizes with monoclinic symmetry, space group P2,, with two magnetically inequivalent stacks in the unit cell. The noncentrosymmetric space group is very unusual for CT-complexes. The optical emission spectra at low temperature are characterized by a strong CT phosphorescence and a weak CT fluorescence and delayed fluorescence.The S, band lies at 22 800 ± 100 cm" 1 , the T, band at 21 200 ± 100 cm" 1 . Above 15 K triplet excitons, moving along the stacks are revealed by ESR. They have a CT character of about 30%, coinciding with that of the shallow X-traps found by ODMR at jow temperatures. A further trap, with zero-field-splitting (zfs) parameters of £> = ±0.0617, E = + 0.0116 cm" 1 has a much larger CT character of 50% as found in the isolated complex in low-temperature glass [1]. A structural model is proposed.

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“…Tetrahalophthalic anhydrides (TXPA) are known to form CT complexes of π···π type with a number of polycyclic aromatic compounds as electron charge acceptors [ 11 , 12 , 13 ]. In this regard, crystals of TXPA, where X = Cl (TCPA), Br (TBPA), and I (TIPA) ( Figure 1 ), have been investigated by X-ray diffraction (XRD) to determine molecular structures of crystals without effects from the formation of CT complexes [ 13 , 14 , 15 , 16 , 17 , 18 ].…”

Section: Introductionmentioning

confidence: 99%

“…In the context of the discussion of noncovalent interactions, X···X (X = Cl, Br, I) [ 13 , 14 , 17 , 18 ] and X···O(acyl) (X = Cl, Br) [ 13 , 14 ] intermolecular short contacts were recognized in X-ray diffraction structures of TXPA. However, it was believed that these contacts play a minor role in the formation of the crystal lattice.…”

Section: Introductionmentioning

confidence: 99%

“…However, it was believed that these contacts play a minor role in the formation of the crystal lattice. The influence of the fused five-membered anhydride ring and the intramolecular steric repulsion of halogen atoms attracts more attention as a promising reason for planar structure distortion and the special crystal patterns of compounds, particularly in the case of TIPA [ 14 , 15 , 17 , 18 ]. Only in one work [ 13 ] the role of these contacts in the formation of the crystal lattice of TBPA had been discussed and the Br···O(acyl) interaction has been identified as a halogen bond.…”

Section: Introductionmentioning

confidence: 99%

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Comparative Structural Study of Three Tetrahalophthalic Anhydrides: Recognition of X···O(anhydride) Halogen Bond and πh···O(anhydride) Interaction

et al. 2021

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Structures of three tetrahalophthalic anhydrides (TXPA: halogen = Cl (TCPA), Br (TBPA), I (TIPA)) were studied by X-ray diffraction, and several types of halogen bonds (HaB) and lone pair···π-hole (lp···πh) contacts were revealed in their structures. HaBs involving the central oxygen atom of anhydride group (further X···O(anhydride) were recognized in the structures of TCPA and TBPA. In contrast, for the O(anhydride) atom of TIPA, only interactions with the π system (π-hole) of the anhydride ring (further lp(O)···πh) were observed. Computational studies by a number of theoretical methods (molecular electrostatic potentials, the quantum theory of atoms in molecules, the independent gradient model, natural bond orbital analyses, the electron density difference, and symmetry-adapted perturbation theory) demonstrated that the X···O(anhydride) contacts in TCPA and TBPA and lp(O)···πh in TIPA are caused by the packing effect. The supramolecular architecture of isostructural TCPA and TBPA was mainly affected by X···O(acyl) and X···X HaBs, and, for TIPA, the main contribution provided I···I HaBs.

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Tetrachlorophthalic anhydride (TCPA), a refinement

Cited by 3 publications

References 3 publications

Quantum-Chemical Insight into Structure–Reactivity Relationship in 4,5,6,7-Tetrahalogeno-1H-benzimidazoles: A Combined X-ray, DSC, DFT/QTAIM, Hirshfeld Surface-Based, and Molecular Docking Approach

Quantum-Chemical Insight into Structure–Reactivity Relationship in 4,5,6,7-Tetrahalogeno-1H-benzimidazoles: A Combined X-ray, DSC, DFT/QTAIM, Hirshfeld Surface-Based, and Molecular Docking Approach

Characterization of the Phenanthrene-Tetrachlorophthalic Anhydride (P/TCPA) 1:1 Charge-Transfer Crystal: Spectroscopic and Structural Investigations

Comparative Structural Study of Three Tetrahalophthalic Anhydrides: Recognition of X···O(anhydride) Halogen Bond and πh···O(anhydride) Interaction

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