Synthesis, Crystal Structure and Intramolecular Interactions of 2-Methyl-3-(2-Methylphenyl)but-1-ene-1,1-dicarbonitrile (MMBD)

Grabowski, SJ; Wilamowski, Jarosław; Osman, Doaa Ahmed; Sepiol, JJ; Rodier, N.

doi:10.1071/ch9960951

Cited by 14 publications

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“…As is widely known, hydrogen-bonded complexes formed by p bonds and proton donors are thus stabilized by the formation of pÁ Á ÁH hydrogen bonds. [249][250][251][252][253][254][255][256][257] However, this statement was not entirely accepted at first, and thereby various works were elaborated in order to discover whether individual atoms or p-electrons can be really considered protons acceptors. In this scenery the neutron diffraction analysis has shown that pÁ Á ÁH interactions are aligned directly at the midpoint of the p bond.…”

Section: Boaz Galdino De Oliveiramentioning

confidence: 99%

Structure, energy, vibrational spectrum, and Bader's analysis of π⋯H hydrogen bonds and H^−δ⋯H^+δdihydrogen bonds

Oliveira

2013

Phys. Chem. Chem. Phys.

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In this paper, the intermolecular structural study asserted by the vibrational analysis in the stretch frequencies of hydrogen bonds (π···H) and dihydrogen bonds (H(-δ)···H(+δ)) have definitively been revisited by means of calculations carried out by Density Functional Theory (DFT) and topological parameters derived from the classic treatise of the Quantum Theory of Atoms in Molecules (QTAIM). As a matter of fact the π···H hydrogen bond is formed between the hydrofluoric acid and the C≡C bond of the acetylene, but the QTAIM calculations revealed a distortion in this interaction due to the formation of the ternary complex C(2)H(2)···2(HF). Although the π bonds of ethylene (C(2)H(4)), propylene (C(2)H(3)(CH(3))), and t-butylene (C(2)H(2)(CH(3))(2)) are considered proton acceptors, two hydrogen-bond types--π···H and C···H--can be observed. Over and above the analysis of the π hydrogen bonds, theoretical arguments also were used to discuss the red-shifts in the stretch frequencies of the binary dihydrogen complexes formed by BeH(2)···HX with X = F, Cl, CN, and CCH. Although a vibrational blue-shift in the stretch frequency of the H-C bond of HCF(3) due to the formation of the BeH(2)···HCF(3) dihydrogen complex was obtained, unmistakable red-shifts were detected in LiH···HCF(3), MgH(2)···HCF(3), and NaH···HCF(3). Moreover, the alkali-halogen bonds were identified in relation to the formation of the trimolecular systems NaH···2(HCF(3)) and NaH···2(HCCl(3)). At last, theoretical calculations and QTAIM molecular integrations were used to study a novel class of dihydrogen-bonded complexes (mC(2)H(5)(+)···nMgH(2) with m = 1 or 2 and n = 1 or 2) based in the insight that MgH(2) can bind with the non-localized hydrogen H(+δ) of the ethyl cation (C(2)H(5)(+)). In an overview, QTAIM calculations were applied to evaluate the molecular topography, charge density, as well as to interpret the shifted frequencies either to red or blue caused by the formation of the hydrogen bonds and dihydrogen bonds.

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Section: Boaz Galdino De Oliveiramentioning

confidence: 99%

Structure, energy, vibrational spectrum, and Bader's analysis of π⋯H hydrogen bonds and H^−δ⋯H^+δdihydrogen bonds

Oliveira

2013

Phys. Chem. Chem. Phys.

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“…Suttor has found C−H···Y H-bonds in some organic crystal structures, and the possibility that a C−H bond with a nonelectronegative carbon atom acts as a proton donor was commonly accepted after the appearance of the study of Taylor and Kennard . X−H···C, X−H···π-electrons, or even C−H···C/π interactions have been also detected and classified as hydrogen bonds. ,, It was pointed out that C−H···Y H-bonds are weak, but electrostatic forces act far beyond the most often applied van der Waals cutoff; hence, the criterion that the H···Y distance should be less than the sum of van der Waals radii fails . The statement that the X−H proton donating bond is elongated within the hydrogen bridge is also not always fulfilled since systems where the proton donating bonds are shortened were found .…”

Section: Introductionmentioning

confidence: 99%

How Short Can the H···H Intermolecular Contact Be? New Findings that Reveal the Covalent Nature of Extremely Strong Interactions

2005

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Ab initio calculations at the MP2/6-311++G(d,p) and MP2/aug-cc-pVDZ//MP2/aug-cc-pVTZ levels have been performed for the following complexes: H2OH+...HBeH, H2OH+...HBeBeH, H2OH+...HBeF, HClOH+...HBeH, Cl2OH+...HBeH, and Cl2OH+...HBeF. For all dimers considered, extremely short H...H intermolecular contacts (1.0-1.3 A) were obtained. These are the shortest intermolecular distances which have ever been reported, with binding energies within the range of 13.7-24.3 kcal/mol (MP2/aug-cc-pVDZ//MP2/aug-cc-pVTZ level). The interaction energies of the complexes analyzed were also extrapolated to the complete basis set (CBS) limit. To explain the nature of such strong interactions, the Bader theory was applied, and the characteristics of the bond critical points (BCPs) were analyzed. It was pointed out that for the major part of the H...H contacts considered here the Laplacian of the electron density at H...H BCP is negative indicating the partly covalent nature of such a connection. The term "covalent character of the hydrogen bond" used sometimes in recent studies is discussed. An analysis of the interaction energy components for dihydrogen bonded systems considered indicates that in contrast to conventional hydrogen bonded systems the attractive electrostatic term is outweighed by the repulsive exchange energy term and that the higher order delocalization energy term is the most important attractive term.

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“…Such interactions are known as nonconventional hydrogen bonds. There are different types of nonconventional hydrogen bonds, for example, H‐bonds with CH bonds as unconventional donors 5–12, those with unconventional acceptors (π electrons within aromatic systems or the other π‐electronic moieties or simple C‐atoms) 13–17, hydrogen bonds with unconventional donors and unconventional acceptors such as CH···C (or CH···π) systems 18–24 and dihydrogen bonds 25–34.…”

Section: Introductionmentioning

confidence: 99%

Influence of substitution on the strength and nature of CH···N hydrogen bond in XCCH···NH₃complexes

Roohi

Bagheri

2011

Int J of Quantum Chemistry

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The effect of substitution on the strength and nature of CHÁ Á ÁN hydrogen bond in XCCHÁ Á ÁNH 3 (X ¼ F, Cl, Br, OH, H, Me) and NCHÁ Á ÁNH 3 complexes were investigated by quantum chemical calculations. Ab initio calculations were performed using MP2 method with a wide range of basis sets. With tacking into account the BSSE and ZPVE, the values of BEs decrease. Replacement of the nonparticipatory hydrogen atom of HCCH by the electronegative atoms (F, Cl, and Br), lead to the BEs increases. The BE corresponding to the replacement of the nonparticipatory hydrogen atom of HCCH by the OH and CH 3 groups decreases. A far greater enhancement of the interaction energy arises from replacement of HCCH by the more acidic HCN. The natural bond orbital analysis and the Bader's quantum theory of atoms in molecules were also used to elucidate the interaction characteristics of these complexes. The electrostatic nature of H-bond interactions is predicted from QTAIM analysis. In addition, the relationship between the isotropic and anisotropic chemical shifts of the bridging hydrogen and binding energy of complexes as well as electron density at NÁ Á ÁH BCPs were investigated.

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Synthesis, Crystal Structure and Intramolecular Interactions of 2-Methyl-3-(2-Methylphenyl)but-1-ene-1,1-dicarbonitrile (MMBD)

Cited by 14 publications

References 0 publications

Structure, energy, vibrational spectrum, and Bader's analysis of π⋯H hydrogen bonds and H^−δ⋯H^+δdihydrogen bonds

Structure, energy, vibrational spectrum, and Bader's analysis of π⋯H hydrogen bonds and H^−δ⋯H^+δdihydrogen bonds

How Short Can the H···H Intermolecular Contact Be? New Findings that Reveal the Covalent Nature of Extremely Strong Interactions

Influence of substitution on the strength and nature of CH···N hydrogen bond in XCCH···NH₃complexes

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Synthesis, Crystal Structure and Intramolecular Interactions of 2-Methyl-3-(2-Methylphenyl)but-1-ene-1,1-dicarbonitrile (MMBD)

Cited by 14 publications

References 0 publications

Structure, energy, vibrational spectrum, and Bader's analysis of π⋯H hydrogen bonds and H−δ⋯H+δdihydrogen bonds

Structure, energy, vibrational spectrum, and Bader's analysis of π⋯H hydrogen bonds and H−δ⋯H+δdihydrogen bonds

How Short Can the H···H Intermolecular Contact Be? New Findings that Reveal the Covalent Nature of Extremely Strong Interactions

Influence of substitution on the strength and nature of CH···N hydrogen bond in XCCH···NH3complexes

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Structure, energy, vibrational spectrum, and Bader's analysis of π⋯H hydrogen bonds and H^−δ⋯H^+δdihydrogen bonds

Structure, energy, vibrational spectrum, and Bader's analysis of π⋯H hydrogen bonds and H^−δ⋯H^+δdihydrogen bonds

Influence of substitution on the strength and nature of CH···N hydrogen bond in XCCH···NH₃complexes