Electronic features and hydrogen bonding capacity of the sulfur acceptor in thioureido-based compounds. Experimental charge density study of 4-methyl-3-thiosemicarbazide
Апстракт
Sulfur atom is generally considered as a weak hydrogen bonding acceptor which is mostly explained by its low electronegativity. This is a background, and motivation, for this study that aims to provide additional insight into electronic features of the sulfur acceptor. The analysis of sulfurs electronic features uses high-resolution, low-temperature X-ray diffraction datasets on 4-methyl-3-thiosemicarbazide (MeTSC) and salicylaldehyde thiosemicarbazone (SalTSC). The total electron density distribution was modeled using Hansen-Coppens multipole model. The fact that MeTSC crystallizes with two crystallographically independent (but chemically equivalent) molecules, engaging in partly different D-H center dot center dot center dot S interactions, has, quite conveniently, enabled the examination of fine effects of the D-H center dot center dot center dot S interactions on the lone pairs electron density of the two S acceptors. The deformation density distribution, topological analysis of th...e total experimental charge density rho(r) and its Laplacian (del(2)rho(r)), and, finally, electrostatic potential all point to the great flexibility of the S acceptor and its ability to adjust to the spatial distribution of the interacting donor groups. Toroidal accumulation of the S lone pairs electron density, strong value of the negative electrostatic potential even at a distance of 3.1 angstrom from the S nucleus, and interpenetration of the van der Waals spheres for the donor and S acceptor atoms are all an indication of sulfurs capacity to simultaneously engage in a greater number of interactions than conventional acceptors such as O and N.
Извор:
CrystEngComm, 2011, 13, 10, 3580-3591Финансирање / пројекти:
- Дизајнирање, синтеза, карактеризација и процена практичне примене координационих и органометалних једињења (RS-MESTD-Basic Research (BR or ON)-172014)
- Рационални дизајн и синтеза биолошки активних и координационих једињења и функционалних материјала, релевантних у (био)нанотехнологији (RS-MESTD-Basic Research (BR or ON)-172035)
DOI: 10.1039/c0ce00760a
ISSN: 1466-8033
WoS: 000289902600048
Scopus: 2-s2.0-79955154042
Колекције
Институција/група
VinčaTY - JOUR AU - Francuski, Bojana M. AU - Novaković, Slađana B. AU - Bogdanović, Goran A. PY - 2011 UR - https://vinar.vin.bg.ac.rs/handle/123456789/4286 AB - Sulfur atom is generally considered as a weak hydrogen bonding acceptor which is mostly explained by its low electronegativity. This is a background, and motivation, for this study that aims to provide additional insight into electronic features of the sulfur acceptor. The analysis of sulfurs electronic features uses high-resolution, low-temperature X-ray diffraction datasets on 4-methyl-3-thiosemicarbazide (MeTSC) and salicylaldehyde thiosemicarbazone (SalTSC). The total electron density distribution was modeled using Hansen-Coppens multipole model. The fact that MeTSC crystallizes with two crystallographically independent (but chemically equivalent) molecules, engaging in partly different D-H center dot center dot center dot S interactions, has, quite conveniently, enabled the examination of fine effects of the D-H center dot center dot center dot S interactions on the lone pairs electron density of the two S acceptors. The deformation density distribution, topological analysis of the total experimental charge density rho(r) and its Laplacian (del(2)rho(r)), and, finally, electrostatic potential all point to the great flexibility of the S acceptor and its ability to adjust to the spatial distribution of the interacting donor groups. Toroidal accumulation of the S lone pairs electron density, strong value of the negative electrostatic potential even at a distance of 3.1 angstrom from the S nucleus, and interpenetration of the van der Waals spheres for the donor and S acceptor atoms are all an indication of sulfurs capacity to simultaneously engage in a greater number of interactions than conventional acceptors such as O and N. T2 - CrystEngComm T1 - Electronic features and hydrogen bonding capacity of the sulfur acceptor in thioureido-based compounds. Experimental charge density study of 4-methyl-3-thiosemicarbazide VL - 13 IS - 10 SP - 3580 EP - 3591 DO - 10.1039/c0ce00760a ER -
@article{ author = "Francuski, Bojana M. and Novaković, Slađana B. and Bogdanović, Goran A.", year = "2011", abstract = "Sulfur atom is generally considered as a weak hydrogen bonding acceptor which is mostly explained by its low electronegativity. This is a background, and motivation, for this study that aims to provide additional insight into electronic features of the sulfur acceptor. The analysis of sulfurs electronic features uses high-resolution, low-temperature X-ray diffraction datasets on 4-methyl-3-thiosemicarbazide (MeTSC) and salicylaldehyde thiosemicarbazone (SalTSC). The total electron density distribution was modeled using Hansen-Coppens multipole model. The fact that MeTSC crystallizes with two crystallographically independent (but chemically equivalent) molecules, engaging in partly different D-H center dot center dot center dot S interactions, has, quite conveniently, enabled the examination of fine effects of the D-H center dot center dot center dot S interactions on the lone pairs electron density of the two S acceptors. The deformation density distribution, topological analysis of the total experimental charge density rho(r) and its Laplacian (del(2)rho(r)), and, finally, electrostatic potential all point to the great flexibility of the S acceptor and its ability to adjust to the spatial distribution of the interacting donor groups. Toroidal accumulation of the S lone pairs electron density, strong value of the negative electrostatic potential even at a distance of 3.1 angstrom from the S nucleus, and interpenetration of the van der Waals spheres for the donor and S acceptor atoms are all an indication of sulfurs capacity to simultaneously engage in a greater number of interactions than conventional acceptors such as O and N.", journal = "CrystEngComm", title = "Electronic features and hydrogen bonding capacity of the sulfur acceptor in thioureido-based compounds. Experimental charge density study of 4-methyl-3-thiosemicarbazide", volume = "13", number = "10", pages = "3580-3591", doi = "10.1039/c0ce00760a" }
Francuski, B. M., Novaković, S. B.,& Bogdanović, G. A.. (2011). Electronic features and hydrogen bonding capacity of the sulfur acceptor in thioureido-based compounds. Experimental charge density study of 4-methyl-3-thiosemicarbazide. in CrystEngComm, 13(10), 3580-3591. https://doi.org/10.1039/c0ce00760a
Francuski BM, Novaković SB, Bogdanović GA. Electronic features and hydrogen bonding capacity of the sulfur acceptor in thioureido-based compounds. Experimental charge density study of 4-methyl-3-thiosemicarbazide. in CrystEngComm. 2011;13(10):3580-3591. doi:10.1039/c0ce00760a .
Francuski, Bojana M., Novaković, Slađana B., Bogdanović, Goran A., "Electronic features and hydrogen bonding capacity of the sulfur acceptor in thioureido-based compounds. Experimental charge density study of 4-methyl-3-thiosemicarbazide" in CrystEngComm, 13, no. 10 (2011):3580-3591, https://doi.org/10.1039/c0ce00760a . .