Michael addition of phenylacetonitrile to the acrylonitrile group leading to diphenylpentanedinitrile. Structural data and theoretical calculations (original) (raw)
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2021
The crystal structure of 2-amino-4-(2,4-dichlorophenyl)-6 phenylnicotinonitrile (ADPN) was determined by single crystal X-ray diffraction. The crystal structure showed two independent molecules with very similar geometric parameters and different environments. Density functional theory (DFT) and DFT dispersion corrected (DFT-D3) calculations were applied to study the structural and chemical properties of ADPN and its dimer. To have a better insight into the properties of the synthesized molecule, quantum chemistry calculations were performed. Based on the calculated results, the dispersion forces have remarkable effects on the stability of ADPN crystal. Moreover, hydrogen bond interactions between ADPN molecules due to molecular orbital interactions can be a driving force for the dimerization process.
Crystal Structure of ( E )-2,3Dihydro2-(R-Phenylacylidene)-1,3,3Trimethyl1 H Indole (R = 4CN, 4Cl)
Journal of Chemical Crystallography, 2011
Two new 1,3,3-trimethyl-2-methylene-2,3-dyhidro-1H-indole derivatives, (E)-2,3-dihydro-2-(4-cyanophenylacylidene)-1,3,3-trimethyl-1H-indole, (I), and (E)-2,3-dihydro-2-(4-chlorophenylacylidene)-1,3,3-trimethyl-1H-indole, (II), have been synthesized and their crystal structure determined by single crystal X-ray diffraction. (I), C20H18N2O, crystallizes in a monoclinic space group, P21/c, with unit cell parameters a = 9.882 (3), b = 15.614(4), c = 11.181(3) Å, β = 106.691(4)°, Z = 4. (II), C19H18Cl N O, crystallizes in a monoclinic space group, P21/n, with unit cell parameters a = 14.6722(19), b = 7.2597(9), c = 16.304(2) Å, β = 111.249
Molecules, 2021
The compounds I (Z)-2-(phenyl)-3-(2,4,5-trimethoxyphenyl)acrylonitrile with one side (2,4,5-MeO-), one symmetrical (2Z,2′Z)-2,2′-(1,4-phenylene)bis(3-(2,4,5-trimethoxyphenyl)acrylonitrile), II (both sides with (2,4,5-MeO-), and three positional isomers with pyridine (Z)-2-(pyridin-2- 3, or 4-yl)-3-(2,4,5-trimethoxyphenyl)acrylonitrile, III–V were synthetized and characterized by UV-Vis, fluorescence, IR, H1-NMR, and EI mass spectrometry as well as single crystal X-ray diffraction (SCXRD). The optical properties were strongly influenced by the solvent (hyperchromic and hypochromic shift), which were compared with the solid state. According to the solvatochromism theory, the excited-state (μe) and ground-state (μg) dipole moments were calculated based on the variation of Stokes shift with the solvent’s relative permittivity, refractive index, and polarity parameters. SCXRD analyses revealed that the compounds I and II crystallized in the monoclinic system with the space group, P21/n a...
We report single crystal X-ray diffraction (hereafter, SCXRD) analyses of derivatives featuring the electron-donor N-ethylcarbazole or the (4-diphenylamino)phenyl moieties associated with a-CN group attached to a double bond. The compounds are (2Z)-3-(4-(diphenylamino)-phenyl)-2-(pyridin-3-yl)prop-2-enenitrile (I), (2Z)-3-(4-(diphenylamino)phenyl)-2-(pyridin-4-yl)-prop-2-enenitrile (II) and (2Z)-3-(9-ethyl-9H-carbazol-3-yl)-2-(pyridin-2-yl)enenitrile (III). SCXRD analyses reveal that I and III crystallize in the monoclinic space groups P2/c with Z' = 2 and C2/c with Z' = 1, respectively. Compound II crystallized in the orthorhombic space group Pbcn with Z' = 1. The molecular packing analysis was conducted to examine the pyridine core effect, depending on the ortho, meta-and para-positions of the nitrogen atom, with respect to the optical properties and number of independent molecules (Z'). It is found that the double bond bearing a diphenylamino moiety introduced properties to exhibit a strong π-π-interaction in the solid state. The compounds were examined to evaluate the effects of solvent polarity, the role of the molecular structure, and the molecular interactions on their self-assembly behaviors. Compound I crystallized with a cell with two conformers, anti and syn, due to interaction with solvent. DFT calculations indicated the anti and syn structures of I are energetically stable (less than 1 eV). Also electrochemical and photophysical properties of the compounds were investigated, as well as the determination of optimization calculations in gas and different solvent (chloroform, cyclohexane, methanol, ethanol, tetrahydrofuran, dichloromethane and dimethyl sulfoxide) in the Gaussian09 program. The effect of solvent by PCM method was also investigated. The frontier HOMO and LUMO energies and gap energies are reported.
Journal of Chemical Crystallography, 2011
The eight-membered {ÁÁÁHOC=O} 2 synthon featured in the crystal structure of 2-amino-4-nitrobenzoic acid (1) is replaced by carboxylic acidÁÁÁN-pyridine hydrogen bonds in its cocrystals with 2,2 0-bipyridine (2/1; 2) and bis(pyridin-2-yl)ketone (1/1; 3) indicating the robust nature of the latter synthon. Disruption of the three-dimensional architecture based on O-HÁÁÁO and N-HÁÁÁO(nitro) hydrogen bonds in (1) is evident in the cocrystals which form supramolecular tubes (2) and chains (3) based on O-HÁÁÁN and N-HÁÁÁO hydrogen bonding. Compound (1) crystallizes in the monoclinic space group P2 1 /n with a = 3.6291(1) Å , b = 7.7339(3) Å , c = 26.561(1) Å , b = 91.385(2)°, and Z = 4. Compound (2) crystallizes in the monoclinic space group C2/c with a = 27.562(3) Å , b = 6.8300(6) Å , c = 12.923(1) Å , b = 110.593(5)°, and Z = 4. Compound (3) crystallizes in the monoclinic space group P2 1 /c with a = 3.795(3) Å , b = 12.024(8) Å , c = 35.65(2) Å , b = 92.131(6)°, and Z = 4 (determined from synchrotron data).
Journal of Molecular Structure, 1999
The IR (4000-400 cm Ϫ1) and Raman (4000-50 cm Ϫ1) spectra of 3-methoxymethylene-2,4-pentanedione (H 3 CO -CHyC (COCH 3) 2) in the liquid and solute forms in various solvents of different polarity were recorded at ambient temperature. Additional IR and Raman spectra were obtained for amorphous and crystalline solid at low temperature. The vibrational spectra revealed that compound exists atleast in two dominant conformers with different polarity and that conformer present in the solid phase is less polar. NMR spectra in various solvents at different temperatures were also obtained.The compound can exist in several conformers as a result of rotation around O-Cy and both yC-C bonds with planar or nonplanar arrangement of the heavy atoms. Semiempirical (AM1, PM3, MNDO, MINDO3) and ab initio using TZP and 6-31G** basis sets calculations were carried out. According to ab initio calculations at least five conformational structures with the methoxy group oriented as anti or syn and carbonyl groups oriented as Z or E towards the CyC double bond were obtained at energy surface. The calculated ab initio and AM1 energies of all conformers suggest as the most stable anti-ZE conformer where Z and E regard of the trans and cis acetyl group, respectively. As the second most stable conformer with energy at least 10 kJ mol Ϫ1 higher was calculated anti-EZ conformer. Assignments of the vibrational spectra for the studied compound were made with the aid of normal coordinate calculations employing scaled ab initio force field constants. The scaled ab initio frequencies as well as calculated energies indicate that the conformer present in the solid phase is anti-ZE.
Trif_Journal of Structural Chemistry Volume 39 issue 3 1998.pdf
UDC 577 + 547.532.783 Molecular parameters of hexaalkoxytriphenylenes with different substituents on the periphery of the triphenylene nucleus of known and hypothetical structures are calculated. The probability of a discophase for compounds of this series is estimated from molecular parameters. Several compounds of this series having polar groups (NO 2, NH2) in the 1 position of the triphenylene nucleus have been synthesized. The compounds synthesized were investigated by thermopolarizing microscopy and X-ray diffraction analysis. The data on the mesomorphism of the new compounds are in good agreement with our prediction that alkoxytriphenylenes with polar groups have a discophase. It is established that introduction of an electron-accepting group at position 1 of the triphenylene nucleus expands the temperature range of eMstence of the discophase to room temperature. On the contrary, introduction of an electron-donating group narrows this interval. Compounds of this series presumably have a hexagonal columnar structure.
Acta Crystallographica Section E Crystallographic Communications
The N,N-dimethylethylamminium unit in N,N-dimethyl-[2-(2,2-diphenyl)-2-prop-2-ynyloxyacetoxy]ethylamine, C21H23NO3 (I), is disordered over two sets of atomic sites having occupancies of 0.880 (3) and 0. 120 (3), but there are no direction-specific interactions between the molecules of (I). The cation in N,N-dimethyl-[2-(2,2-diphenyl)-2-prop-2-ynyloxyacetoxy]ethylammonium 2,4,6-trinitrophenolate (picrate), C21H24NO3 +·C6H2N3O7 − (II), shows a similar type of disorder, with occupancies of 0.654 (11) and 0.346 (11), although the overall conformation of the cation in (II) is different from that in the neutral (I). The component ions are are linked by an almost planar three-centre N—H...(O)2 hydrogen bond, and the ion pairs are further linked by a combination of three C—H...O hydrogen bonds to form sheets. Comparisons are made with some related structures.
Arkivoc, 2008
In this work we present the synthesis of 4,4'-[1,4-phenylene-bis(azanediyl)]dipent-3-en-2-one. Evidence is proposed for the presence of various tautomers of this molecule which are complemented with theoretical density functional theory (DFT)-B3LYP/6-31G* calculations to characterize the potential energy surface of these species. The experimentally observed 3b isomer crystallizes as an orthorhombic Pbcn structure; a = 10.8412(10) Å, b = 8.9205(7)Å, c = 14.9949(13)Å, V = 1450.1(2) Å 3 , Z = 4 with a final R value is 0.038. From our X-Ray crystallographic analysis an intramolecular hydrogen N-H···O interaction is observed.