Electronic features and hydrogen bonding capacity of the sulfur acceptor in thioureido-based compounds. Part 2. Further insight by theoretical charge density study

Novaković, Sladjana B.; Ostojić, Bojana; Francuski, Djordje; Bogdanović, Goran A.

doi:10.1016/j.comptc.2015.05.024

Cited by 3 publications

(3 citation statements)

References 46 publications

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“…The wave function was obtained using the self-consistent-field (SCF) calculations with the B3LYP/6-31G** level of theory. The 6-31G** basis set was chosen due to the good fit of the previously calculated N–H···S cohesive energies ( E coh ), and interaction energies calculated with the accurate CCSD(T) method (coupled-cluster singles and doubles augmented by a perturbational correction for connected triple excitations). The shrinking factors (IS1, IS2, and IS3) along with the reciprocal lattice vectors were set to 8.…”

Section: Methodsmentioning

confidence: 99%

Charge Density Analysis of 2-Pyridineformamide N(4)-Methylthiosemicarbazone (Z′ = 4): Role of an Enhanced N–H···S Thioureido Dimer

Novaković

Francuski

Bogdanović

2017

Crystal Growth & Design

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Charge density distribution in 2-pyridineformamide N(4)-methylthiosemicarbazone (TSC4) has been determined using high-resolution X-ray diffraction data (100 K) and Hansen−Coppens multipole formalism. The results are interpreted in terms of Bader's quantum theory of atoms in molecules (QTAIM), electrostatic potential analysis, and theoretical calculations (CRYSTAL09). The study highlights the molecular dissimilarity at the electronic level. The N−H•••S interactions have a dominant role in stabilization of the TSC4 crystal structure. As each of the four S acceptors simultaneously engages in several interactions, the focus of study is on the lone pairs' electron density of these acceptors which is particularly able to adjust to the various spatial distributions of the interacting donor groups. The main structural feature of TSC4 is the formation of specific N−H•••S bonded dimers between two pairs of independent molecules. These dimers are the main building block in the crystal structure, and with the two additional N−H•••S contacts they represent a significant enhancement of a typical R 2 2 (8) dimer synthon which dominates among the thioureido-based crystal structures. Two TSC4 dimers are structurally very similar and exhibit considerable cohesive energy (−20.8 and −21.4 kcal/mol). This type of dimer is the only structural motif that is common for S acceptors of all four independent molecules.

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Section: Methodsmentioning

confidence: 99%

Charge Density Analysis of 2-Pyridineformamide N(4)-Methylthiosemicarbazone (Z′ = 4): Role of an Enhanced N–H···S Thioureido Dimer

Novaković

Francuski

Bogdanović

2017

Crystal Growth & Design

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“…Furthermore, the electronic structure of such compounds is not less interesting. For example, in their series of experimental works, Bogdanović et al ,,, reported the sulfur atom’s ability to participate in various hydrogen bonds, including rather strong N–H···S interactions, and the consequent formation of a toroidal shape of deformation ED. As shown by the CSD analysis in work, more than 40% of compounds with the thiourea fragment contain a sulfur atom involved in four or more hydrogen bonds.…”

Section: Introductionmentioning

confidence: 99%

“…Furthermore, the electronic structure of such compounds is not less interesting. For example, in their series of experimental works, Bogdanovićet al 35,40,44,45 reported the sulfur atom's ability to participate in various hydrogen bonds, including rather strong N−H•••S interactions, and the consequent formation of a toroidal shape of deformation ED.…”

Section: ■ Introductionmentioning

confidence: 99%

X-ray Charge Density Study of the Drug Methimazole with Z′ = 2: Differences in the Electronic Structure of the Thiourea Core due to Crystal Packing Effects

Shteingolts

Fayzullin

2020

Crystal Growth & Design

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Herein we present a detailed experimental charge-density study for the low-temperature polymorph of the antithyroid drug methimazole crystallized with two crystallographically independent molecules lacking conformational freedom. Quantum-topological analysis of experimental electron density allowed us to detect the distinctive differences in the electron distribution within their thiourea groups, arising primarily from crystal packing effects. The sulfur atom S(1a) features two separate regions of positive deformation density, while the other atom S(1b) is found to be more diffuse with positive density taking a toroidal form. In contrast to S(1a), the couple of the lone pairs of S(1b) derived by nonbonding charge concentrations takes a more significant turn relative to the molecular plane and proves to be distorted. We also report an ambiguous electronic structure of the heteroatoms, i.e., the appearance of "false" Laplacian critical points (CPs) (3, +3) or splitting of true ones, which is caused by neglecting or excessive use of Gram−Charlier coefficients. Further, the turn of lone pairs, behavior of source function within the thiourea fragment, and atomic charges indicate decreased bond order of the formally double CS bond and increased contribution of the [CH 3 −]N (+) C−S (−) canonical structure into π-conjugation. Moreover, intermolecular hydrogen bonds N−H•••S and head-to-head interactions CS•••SC are described.

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Versatile coordination chemistry of thiosemicarbazide and its non-Schiff base derivatives

Leovac,

Novaković

2024

Journal of Molecular Structure

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Electronic features and hydrogen bonding capacity of the sulfur acceptor in thioureido-based compounds. Part 2. Further insight by theoretical charge density study

Cited by 3 publications

References 46 publications

Charge Density Analysis of 2-Pyridineformamide N(4)-Methylthiosemicarbazone (Z′ = 4): Role of an Enhanced N–H···S Thioureido Dimer

Charge Density Analysis of 2-Pyridineformamide N(4)-Methylthiosemicarbazone (Z′ = 4): Role of an Enhanced N–H···S Thioureido Dimer

X-ray Charge Density Study of the Drug Methimazole with Z′ = 2: Differences in the Electronic Structure of the Thiourea Core due to Crystal Packing Effects

Versatile coordination chemistry of thiosemicarbazide and its non-Schiff base derivatives

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