Synthesis, spectroscopic characterization, X-ray structure and DFT calculations of Ni(II)bis(3,4 dimethoxybenzoate)bis(nicotinamide) dihydrate

2017 ◽  
Vol 23 (2) ◽  
pp. 115-123
Author(s):  
Elif Çelenk Kaya ◽  
Afşin Ahmet Kaya ◽  
Zeynep Demircioğlu ◽  
Orhan Büyükgüngör
Keyword(s):  
Single Crystal ◽  
Density Functional ◽  
Function Analysis ◽  
Population Analysis ◽  
Density Functional Theory Method ◽  
Basis Set ◽  
Monoclinic Space Group ◽  
Mulliken Population ◽  
X Ray ◽  
Distorted Octahedral

AbstractA single crystal of Ni(II)bis(3,4 dimethoxybenzoate)bis(nicotinamide) dihydrate, formulated as C30H34N4NiO12 (I), was characterized in the solid state by infra-red (IR), ultra-violet (UV) and single crystal X-ray diffraction analysis at 296 K as mononuclear with a distorted octahedral stereochemistry. The complex consists of a six-coordinate Nickel atom in a distorted octahedral environment constructed from two N atoms and four O atoms and crystallizes in the monoclinic space group C 2/c with a=27.7680(16) Å, b=8.5748(3) Å, c=17.8018(9) Å, α=90°, β=108.154(4)°, γ=90°, Z=4. The molecular structure and geometry was also optimized using the B3LYP density functional theory method employing the 6-31G(d) basis set. The molecular electrostatic potential (MEP), frontier molecular orbitals (FMO) analysis, nonlinear optical properties (NLO) and natural bond analysis (NBO), Mulliken population analyis, natural population analysis (NPA) and Fukui function analysis were also described.

X-ray and DFT Investigation of (E)-4-bromo-5-methoxy-2-((o-tolylimino)methyl)phenol Compound

2018 ◽  
pp. 454-461
Keyword(s):  
Density Functional ◽  
Theoretical Calculations ◽  
Population Analysis ◽  
Diffraction Method ◽  
Dft Method ◽  
Basis Set ◽  
X Ray Diffraction ◽  
Mulliken Population ◽  
Charge Delocalization ◽  
X Ray

(E)-4-bromo-5-methoxy-2-((o-tolylimino)methyl)phenol was investigated by experimental and theoretical methodologies. The solid state molecular structure was determined by X-ray diffraction method. All theoretical calculations were performed by density functional theory (DFT) method by using B3LYP/6-31G(d,p) basis set. The titled compound showed the preference of enol form, as supported by X-ray diffraction method. The geometric and molecular properties were compaired for both enol-imine and keto-amine forms for title compound. Stability of the molecule arises from hyperconjugative interactions, charge delocalization and intramolecular hydrogen bond has been analyzed using natural bond orbital (NBO) analysis. Mulliken population method and natural population analysis (NPA) have been studied. Also, condensed Fukui function and relative nucleophilicity indices calculated from charges obtained with orbital charge calculation methods (NPA). Molecular electrostatic potential (MEP) and non linear optical (NLO) properties are also examined.

The crystal structure of Bis[2-(pyridin-2-ylamino)-4-(pyridin-2-yl)thiazole]iron(II) Bis(tetrafluoroborate) trihydrate

1984 ◽  
Vol 37 (2) ◽  
pp. 443 ◽  
Author(s):  
AT Baker ◽  
HA Goodwin ◽  
AD Rae
Keyword(s):  
Crystal Structure ◽  
Single Crystal ◽  
Complex Cation ◽  
Monoclinic Space Group ◽  
Octahedral Structure ◽  
Space Group ◽  
X Ray ◽  
Disordered Structure ◽  
Distorted Octahedral ◽  
A Cell

The crystal structure of an iron(II) complex of 2-(pyridin-2-ylamino)-4-(pyridin-2-yl)tliazoe (paptH) has been determined by single-crystal X-ray diffractometry. [Fe(paptH)2] [BF4]2.3H2O is monoclinic, space group P21/c, with Z = 4 in a cell of dimensions a 8.968(6), b 9.038(4), c 41.15(2)�, β 94.81(2)�. The disordered structure was refined to a residual R 0.0826 for 2549 observed reflections. The ligands and anions are orientationally disordered, and the waters of crystallization are positionally disordered. Comprehensive constrained refinement, with 220 parameters for 139 atom positions, produced reliable geometry. The complex cation has a distorted octahedral structure of meridional configuration with both paptH ligands functioning as tridentates.

scholarly journals The Molecular Mechanism of the Formation of Four-Membered Cyclic Nitronates and Their Retro (3 + 2) Cycloaddition: A DFT Mechanistic Study

Molecules ◽  
2021 ◽  
Vol 26 (16) ◽  
pp. 4786
Author(s):  
Agnieszka Kącka-Zych
Keyword(s):  
Density Functional ◽  
Function Analysis ◽  
Population Analysis ◽  
Density Functional Theory Method ◽  
Mechanistic Study ◽  
Functional Theory ◽  
Tert Butyl ◽  
The Density Functional Theory ◽  
One Step ◽  
Butyl Ketone

In the present work, the formation of the four-membered cyclic nitronates and the retro (3 + 2) cycloaddition (retro-32CA) reaction of the 4H-[1,2]oxazete 2-oxide were studied using the density functional theory method at the MPWB1K/6-311G(d,p) theoretical level. The electronic structure of 3-tert-butyl-4,4-dimethyl-1,2-dinitro-pent-2-ene was known through electron localization function analysis, natural population analysis, and molecular electrostatic potential analysis. The formation of 4,4-di-tert-butyl-3-nitromethyl-4H-[1,2]oxazete 2-oxide proceeds through a one-step mechanism. The mechanism of the retro-32CA leading to di-tert-butyl ketone and nitrile oxide derivative should be described as an asynchronous two-stage one-step process. The bonding evolution theory study was carried out to clarify the mechanisms of the formation of 4H-[1,2]oxazete 2-oxide and their retro-32CA.

Molecular Structural and Vibrational Spectroscopic Assignments of n5-(4-Methoxyphenyl)-3-(1-methylindol-3-yl)-isoxazole using DFT Theory Calculations

2019 ◽  
Vol 4 (3) ◽  
pp. 147-151
Author(s):  
J. Jani Matilda ◽  
T.F. Abbs Fen Reji
Keyword(s):  
Molecular Orbital ◽  
Density Functional ◽  
Population Analysis ◽  
Nbo Analysis ◽  
Basis Set ◽  
Atomic Charges ◽  
Dft Methods ◽  
Mulliken Population ◽  
B3lyp Method ◽  
Experimental Values

In an effort to evaluate and design fast, accurate density functional theory (DFT) methods for 5-(4- methoxyphenyl)-3-(1-methylindol-3yl)isoxazole compound was done using Gaussion’ 09 program package using B3LYP method with the 6-31G basis set, which has been successfully applied in order to derive the optimized geometry, bonding features, harmonic vibrational wave numbers, NBO analysis and Mulliken population analysis on atomic charges in the ground state. Optimized geometries of the molecule have been described and collate with the experimental values. The experimental atomic charges demonstrates adequate concurrence with the theoretical prediction from DFT. The theoretical spectra values have been interpreted and compared with the FT-IR spectra. The calculated highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energy gaps also confirm that charge transfer takes place within the molecule.

scholarly journals Structure of (E)-N-((5-Nitrothiophen-2-YL)Methylene)-3-(Trifluoromethyl)Aniline

2014 ◽  
Vol 70 (a1) ◽  
pp. C997-C997
Author(s):  
Özlem Deveci ◽  
Sümeyye Gümüş ◽  
Erbil Agˇar
Keyword(s):  
Molecular Structure ◽  
Hydrogen Bonds ◽  
Title Compound ◽  
Density Functional ◽  
Theoretical Calculations ◽  
Molecular Geometry ◽  
Basis Set ◽  
Monoclinic Space Group ◽  
X Ray Diffraction ◽  
X Ray

The Schiff base compound, C12H7N2O2F3S, has been synthesized and characterized by IR, UV-Vis, 1H-NMR, 13C-NMR and single-crystal X-ray diffraction (XRD) and elemental analysis. The compound, an Ortep-3 [1] view of which is shown in Fig. 1, crystallizes in the monoclinic space group P-1 with a= 7.5700(11) Å, b= 12.8280(16) Å, c= 13.0170(16) Å, α= 89.295(10)o, β= 88.691(11)o, γ= 82.246(11)o and Z=4 in the unit cell. The molecular structure is stabilized by C-H...O and C-H...F intramolecular hydrogen bonds and molecules are linked through intermolecular C-H...O and C-H...F type hydrogen bonds and C-H...Cg (π-ring) interaction. The molecular geometry from X-ray determination of the title compound in the ground state has been compared using the Hartre-Fock (HF) and density functional theory (DFT/B3LYP) [2] with 6-31G(d) [3] basis set. The results of the optimized molecular structure are exhibited and compared with the experimental X-ray diffraction. To determine conformational flexibility, molecular energy profile of the title compound was obtained by B3LYP with the 6-31G(d) basis set calculations with respect to selected degree of torsional freedom, which was varied from –1800to +1800in steps of 100. In addition, molecular electrostatic potential (MEP) distribution and frontier molecular orbitals (FMOs) properties of the title molecule were investigated by theoretical calculations at the B3LYP/6-31G (d) level. Figure 1. Ortep 3 diagram of the title compound. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii.

scholarly journals X-ray diffraction and Density Functional Theory based structural analyses of 2-phenyl-4-(prop-2-yn-1-yl)-1,2,4-triazolone

2021 ◽  
Vol 12 (4) ◽  
pp. 459-468
Author(s):  
Shilpa Mallappa Somagond ◽  
Ahmedraza Mavazzan ◽  
Suresh Fakkirappa Madar ◽  
Madivalagouda Sannaikar ◽  
Shankar Madan Kumar ◽  
...  
Keyword(s):  
Density Functional Theory ◽  
Density Functional ◽  
Energy Gap ◽  
Basis Set ◽  
Frontier Molecular Orbital ◽  
Geometrical Parameters ◽  
Monoclinic Space Group ◽  
X Ray Diffraction ◽  
Functional Theory ◽  
X Ray

This study is composed of X-ray diffraction and Density Functional Theory (DFT) based molecular structural analyses of 2-phenyl-4-(prop-2-yn-1-yl)-2,4-dihydro-3H-1,2,4-triazol-3-one (2PPT). Crystal data for C11H9N3O: Monoclinic, space group P21/c (no. 14), a = 7.8975(2) Å, b = 11.6546(4) Å, c = 11.0648(3) Å, β = 105.212(2)°, V = 982.74(5) Å3, Z = 4, T = 296.15 K, μ(MoKα) = 0.091 mm-1, Dcalc = 1.346 g/cm3, 13460 reflections measured (5.174° ≤ 2Θ ≤ 64.72°), 3477 unique (Rint = 0.0314, Rsigma = 0.0298) which were used in all calculations. The final R1 was 0.0470 (I > 2σ(I)) and wR2 was 0.1368 (all data). The experimentally determined data was supported by theoretically optimized calculations processed with the help of Hartree-Fock (HF) technique and Density Functional Theory with the 6-311G(d,p) basis set in the ground state. Geometrical parameters (Bond lengths and angles) as well as spectroscopic (FT-IR, 1H NMR, and 13C NMR) properties of 2PPT molecule has been optimized theoretically and compared with the experimentally obtained results. Hirshfeld surface analysis with 2D fingerprinting plots was used to figure out the possible and most significant intermolecular interactions. The electronic characterizations such as molecular electrostatic potential map (MEP) and Frontier molecular orbital (FMO) energies have been studied by DFT/B3LYP approach. The MEP imparted the detailed information regarding electronegative and electropositive regions across the molecule. The HOMO-LUMO energy gap as high as 5.3601 eV was found to be responsible for the high kinetic stability of the 2PPT.

DFT investigation on interaction of chlorine with In2O3 nanostructures

2015 ◽  
Vol 93 (11) ◽  
pp. 1249-1260 ◽  
Author(s):  
V. Nagarajan ◽  
R. Chandiramouli
Keyword(s):  
Density Functional ◽  
Energy Gap ◽  
Population Analysis ◽  
Average Energy ◽  
Adsorption Properties ◽  
Basis Set ◽  
Mixed Gas ◽  
Mulliken Population ◽  
Adsorption Sites ◽  
Homo Lumo

The structural, electronic, and adsorption properties of chlorine on pristine, tin-, aluminum-, and fluorine-substituted In2O3 nanostructures are successfully optimized and computed using density functional theory along with the B2LYP/LanL2DZ basis set. The electronic properties of pristine, tin-, aluminum-, and fluorine-substituted In2O3 nanostructures are discussed in terms of ionization potential, HOMO–LUMO gap, and electron affinity. The dipole moment and point symmetry group of In2O3 nanostructures are also reported. The structural stability of pristine, tin-, aluminum-, and fluorine-substituted In2O3 nanostructures are investigated in terms of formation energy. The adsorption properties of chlorine on In2O3 are studied and the most appropriate adsorption sites of Cl2 on In2O3 nanostructures are reported. The adsorption properties of hydrogen on In2O3 nanostructures are also investigated and inferred that In2O3 exhibits good sensing characteristics towards hydrogen. The adsorbed energy, HOMO–LUMO gap, Mulliken population analysis, and average energy gap variation are used to identify the prominent adsorption site of Cl2 on In2O3 material. The substitution of fluorine in In2O3 nanostructures enhances the Cl2 adsorption properties in the mixed gas atmosphere.

scholarly journals Understanding the reaction mechanism of the regioselective piperidinolysis of aryl 1-(2,4-dinitronaphthyl) ethers in DMSO: Kinetic and DFT studies

2021 ◽  
Vol 46 ◽  
pp. 146867832110274
Author(s):  
Yasmen M Moghazy ◽  
Nagwa MM Hamada ◽  
Magda F Fathalla ◽  
Yasser R Elmarassi ◽  
Ezzat A Hamed ◽  
...  
Keyword(s):  
Carbon Atom ◽  
Density Functional ◽  
Function Analysis ◽  
Density Functional Theory Method ◽  
Activation Parameters ◽  
Kinetic Studies ◽  
Nucleophilic Attack ◽  
Common Mechanism ◽  
Slow Step ◽  
Rate Determining Step

Reactions of aryl 1-(2,4-dinitronaphthyl) ethers with piperidine in dimethyl sulfoxide at 25oC resulted in substitution of the aryloxy group at the ipso carbon atom. The reaction was measured spectrophotochemically and the kinetic studies suggested that the titled reaction is accurately third order. The mechanism is began by fast nucleophilic attack of piperidine on C1 to form zwitterion intermediate (I) followed by deprotonation of zwitterion intermediate (I) to the Meisenheimer ion (II) in a slow step, that is, SB catalysis. The regular variation of activation parameters suggested that the reaction proceeded through a common mechanism. The Hammett equation using reaction constant σo values and Brønsted coefficient value showed that the reaction is poorly dependent on aryloxy substituent and the reaction was significantly associative and Meisenheimer intermediate-like. The mechanism of piperidinolysis has been theoretically investigated using density functional theory method using B3LYP/6-311G(d,p) computational level. The combination between experimental and computational studies predicts what mechanism is followed either through uncatalyzed or catalyzed reaction pathways, that is, SB and SB-GA. The global parameters of the reactants, the proposed activated complexes, and the local Fukui function analysis explained that C1 carbon atom is the most electrophilic center of ether. Also, kinetics and theoretical calculation of activation energies indicated that the mechanism of the piperidinolysis passed through a two-step mechanism and the proton transfer process was the rate determining step.

The first proof of protonated anion tetrahedra in the tsumcorite-type compounds

2004 ◽  
Vol 68 (5) ◽  
pp. 757-767 ◽  
Author(s):  
T. Mihajlović ◽  
H. Effenberger
Keyword(s):  
Crystal Structure ◽  
Hydrothermal Synthesis ◽  
Single Crystal ◽  
Diffraction Data ◽  
Title Compound ◽  
Monoclinic Space Group ◽  
X Ray Diffraction ◽  
Hydrogen Atoms ◽  
Synthetic Compounds ◽  
X Ray

AbstractHydrothermal synthesis produced the new compound SrCo2(AsO4)(AsO3OH)(OH)(H2O). The compound belongs to the tsumcorite group (natural and synthetic compounds with the general formula M(1)M(2)2(XO4)2(H2O,OH)2; M(1)1+,2+,3+ = Na, K, Rb, Ag, NH4, Ca, Pb, Bi, Tl; M(2)2+,3+ = Al, Mn3+, Fe3+, Co, Ni, Cu, Zn; and X5+,6+ = P, As, V, S, Se, Mo). It represents (1) the first Sr member, (2) the until now unknown [7]-coordination for the M(1) position, (3) the first proof of (partially) protonated arsenate groups in this group of compounds, and (4) a new structure variant.The crystal structure of the title compound was determined using single-crystal X-ray diffraction data. The compound is monoclinic, space group P21/a, with a = 9.139(2), b = 12.829(3), c = 7.522(2) Å, β = 114.33(3)°, V = 803.6(3) Å3, Z = 4 [wR2 = 0.065 for 3530 unique reflections]. The hydrogen atoms were located experimentally.

Thermal-induced transformation of glutamic acid to pyroglutamic acid and self-cocrystallization: a charge–density analysis

2022 ◽  
Vol 78 (2) ◽  
Author(s):  
Sehrish Akram ◽  
Arshad Mehmood ◽  
Sajida Noureen ◽  
Maqsood Ahmed
Keyword(s):  
Hydrogen Bonds ◽  
Glutamic Acid ◽  
Single Crystal ◽  
Diffraction Data ◽  
Density Functional ◽  
Quantitative Estimation ◽  
Topological Analysis ◽  
Pyroglutamic Acid ◽  
X Ray Diffraction ◽  
X Ray

Thermal-induced transformation of glutamic acid to pyroglutamic acid is well known. However, confusion remains over the exact temperature at which this happens. Moreover, no diffraction data are available to support the transition. In this article, we make a systematic investigation involving thermal analysis, hot-stage microscopy and single-crystal X-ray diffraction to study a one-pot thermal transition of glutamic acid to pyroglutamic acid and subsequent self-cocrystallization between the product (hydrated pyroglutamic acid) and the unreacted precursor (glutamic acid). The melt upon cooling gave a robust cocrystal, namely, glutamic acid–pyroglutamic acid–water (1/1/1), C5H7NO3·C5H9NO4·H2O, whose structure has been elucidated from single-crystal X-ray diffraction data collected at room temperature. A three-dimensional network of strong hydrogen bonds has been found. A Hirshfeld surface analysis was carried out to make a quantitative estimation of the intermolecular interactions. In order to gain insight into the strength and stability of the cocrystal, the transferability principle was utilized to make a topological analysis and to study the electron-density-derived properties. The transferred model has been found to be superior to the classical independent atom model (IAM). The experimental results have been compared with results from a multipolar refinement carried out using theoretical structure factors generated from density functional theory (DFT) calculations. Very strong classical hydrogen bonds drive the cocrystallization and lend stability to the resulting cocrystal. Important conclusions have been drawn about this transition.

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