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Influence of C-H/X (X = S, Cl, N, Pt/Pd) Interactions on the Molecular and Crystal Structures of Pt(II) and Pd(II) Complexes with Thiomorpholine-4-carbonitrile: Crystallographic, Thermal, and DFT Study

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2020
Authors
Ristić, Predrag
Blagojević, Vladimir A.
Janjić, Goran
Rodić, Marko
Vulić, Predrag J.
Donnard, Morgan
Gulea, Mihaela
Chylewska, Agnieszka
Makowski, Mariusz
Todorović, Tamara
Filipović, Nenad
Article (Published version)
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Abstract
Pt(II) and Pd(II) complexes (1 and 2, respectively) with thiomorpholine-4-carbonitrile (TM-CN), an N-substituted thiomorpholine derivative, were synthesized from tetrachlorido precursors in water. Structural analysis has shown that 1 represents the first monomeric metal complex with this ligand type with an axial M-S bond with respect to the TM-CN ring chair conformation, while in 2 a typical equatorial M-S bond position with respect to the ring chair conformation was observed. A detailed DFT investigation revealed that axial conformers are more stable for molecular forms of both metals, while intermolecular interactions in the crystals stabilize the axial conformer for Pt(II) and the equatorial conformer for Pd(II). The magnitude of this stabilization in the case of 2 is large enough to change the most stable axial conformer in the molecular form to the equatorial conformer in the crystal. Further investigation of the strength of individual intermolecular interactions revealed signifi...cant differences of some interactions between the two structures. The likely cause of the difference in the crystal structures of experimentally obtained complexes is the fact that 1 and 2 exhibit different dominant interactions: C-H/M and C-H/S are more dominant in 1 and C-H/Cl interactions are more dominant in 2. In addition, DFT calculations have shown that while the axial position of the Pt-S bond with respect to the ring chair conformation results in a significantly shorter C-H/Pt interaction distance than that in the hypothetical equatorial conformer, there is very little difference in C-H/Pd interaction distances in conformers with axial and equatorial positions of Pd-S bond with respect to the ring chair conformation.

Source:
Crystal Growth & Design, 2020, 20, 5, 3018-3033
Publisher:
  • Amer Chemical Soc, Washington
Funding / projects:
  • Directed synthesis, structure and properties of multifunctional materials (RS-172057)

DOI: 10.1021/acs.cgd.9b01661

ISSN: 1528-7483

WoS: 000535174000024

Scopus: 2-s2.0-85089237632
[ Google Scholar ]
3
3
URI
http://aspace.agrif.bg.ac.rs/handle/123456789/5373
Collections
  • Radovi istraživača / Researchers’ publications
Institution/Community
Poljoprivredni fakultet
TY  - JOUR
AU  - Ristić, Predrag
AU  - Blagojević, Vladimir A.
AU  - Janjić, Goran
AU  - Rodić, Marko
AU  - Vulić, Predrag J.
AU  - Donnard, Morgan
AU  - Gulea, Mihaela
AU  - Chylewska, Agnieszka
AU  - Makowski, Mariusz
AU  - Todorović, Tamara
AU  - Filipović, Nenad
PY  - 2020
UR  - http://aspace.agrif.bg.ac.rs/handle/123456789/5373
AB  - Pt(II) and Pd(II) complexes (1 and 2, respectively) with thiomorpholine-4-carbonitrile (TM-CN), an N-substituted thiomorpholine derivative, were synthesized from tetrachlorido precursors in water. Structural analysis has shown that 1 represents the first monomeric metal complex with this ligand type with an axial M-S bond with respect to the TM-CN ring chair conformation, while in 2 a typical equatorial M-S bond position with respect to the ring chair conformation was observed. A detailed DFT investigation revealed that axial conformers are more stable for molecular forms of both metals, while intermolecular interactions in the crystals stabilize the axial conformer for Pt(II) and the equatorial conformer for Pd(II). The magnitude of this stabilization in the case of 2 is large enough to change the most stable axial conformer in the molecular form to the equatorial conformer in the crystal. Further investigation of the strength of individual intermolecular interactions revealed significant differences of some interactions between the two structures. The likely cause of the difference in the crystal structures of experimentally obtained complexes is the fact that 1 and 2 exhibit different dominant interactions: C-H/M and C-H/S are more dominant in 1 and C-H/Cl interactions are more dominant in 2. In addition, DFT calculations have shown that while the axial position of the Pt-S bond with respect to the ring chair conformation results in a significantly shorter C-H/Pt interaction distance than that in the hypothetical equatorial conformer, there is very little difference in C-H/Pd interaction distances in conformers with axial and equatorial positions of Pd-S bond with respect to the ring chair conformation.
PB  - Amer Chemical Soc, Washington
T2  - Crystal Growth & Design
T1  - Influence of C-H/X (X = S, Cl, N, Pt/Pd) Interactions on the Molecular and Crystal Structures of Pt(II) and Pd(II) Complexes with Thiomorpholine-4-carbonitrile: Crystallographic, Thermal, and DFT Study
EP  - 3033
IS  - 5
SP  - 3018
VL  - 20
DO  - 10.1021/acs.cgd.9b01661
ER  - 
@article{
author = "Ristić, Predrag and Blagojević, Vladimir A. and Janjić, Goran and Rodić, Marko and Vulić, Predrag J. and Donnard, Morgan and Gulea, Mihaela and Chylewska, Agnieszka and Makowski, Mariusz and Todorović, Tamara and Filipović, Nenad",
year = "2020",
abstract = "Pt(II) and Pd(II) complexes (1 and 2, respectively) with thiomorpholine-4-carbonitrile (TM-CN), an N-substituted thiomorpholine derivative, were synthesized from tetrachlorido precursors in water. Structural analysis has shown that 1 represents the first monomeric metal complex with this ligand type with an axial M-S bond with respect to the TM-CN ring chair conformation, while in 2 a typical equatorial M-S bond position with respect to the ring chair conformation was observed. A detailed DFT investigation revealed that axial conformers are more stable for molecular forms of both metals, while intermolecular interactions in the crystals stabilize the axial conformer for Pt(II) and the equatorial conformer for Pd(II). The magnitude of this stabilization in the case of 2 is large enough to change the most stable axial conformer in the molecular form to the equatorial conformer in the crystal. Further investigation of the strength of individual intermolecular interactions revealed significant differences of some interactions between the two structures. The likely cause of the difference in the crystal structures of experimentally obtained complexes is the fact that 1 and 2 exhibit different dominant interactions: C-H/M and C-H/S are more dominant in 1 and C-H/Cl interactions are more dominant in 2. In addition, DFT calculations have shown that while the axial position of the Pt-S bond with respect to the ring chair conformation results in a significantly shorter C-H/Pt interaction distance than that in the hypothetical equatorial conformer, there is very little difference in C-H/Pd interaction distances in conformers with axial and equatorial positions of Pd-S bond with respect to the ring chair conformation.",
publisher = "Amer Chemical Soc, Washington",
journal = "Crystal Growth & Design",
title = "Influence of C-H/X (X = S, Cl, N, Pt/Pd) Interactions on the Molecular and Crystal Structures of Pt(II) and Pd(II) Complexes with Thiomorpholine-4-carbonitrile: Crystallographic, Thermal, and DFT Study",
pages = "3033-3018",
number = "5",
volume = "20",
doi = "10.1021/acs.cgd.9b01661"
}
Ristić, P., Blagojević, V. A., Janjić, G., Rodić, M., Vulić, P. J., Donnard, M., Gulea, M., Chylewska, A., Makowski, M., Todorović, T.,& Filipović, N.. (2020). Influence of C-H/X (X = S, Cl, N, Pt/Pd) Interactions on the Molecular and Crystal Structures of Pt(II) and Pd(II) Complexes with Thiomorpholine-4-carbonitrile: Crystallographic, Thermal, and DFT Study. in Crystal Growth & Design
Amer Chemical Soc, Washington., 20(5), 3018-3033.
https://doi.org/10.1021/acs.cgd.9b01661
Ristić P, Blagojević VA, Janjić G, Rodić M, Vulić PJ, Donnard M, Gulea M, Chylewska A, Makowski M, Todorović T, Filipović N. Influence of C-H/X (X = S, Cl, N, Pt/Pd) Interactions on the Molecular and Crystal Structures of Pt(II) and Pd(II) Complexes with Thiomorpholine-4-carbonitrile: Crystallographic, Thermal, and DFT Study. in Crystal Growth & Design. 2020;20(5):3018-3033.
doi:10.1021/acs.cgd.9b01661 .
Ristić, Predrag, Blagojević, Vladimir A., Janjić, Goran, Rodić, Marko, Vulić, Predrag J., Donnard, Morgan, Gulea, Mihaela, Chylewska, Agnieszka, Makowski, Mariusz, Todorović, Tamara, Filipović, Nenad, "Influence of C-H/X (X = S, Cl, N, Pt/Pd) Interactions on the Molecular and Crystal Structures of Pt(II) and Pd(II) Complexes with Thiomorpholine-4-carbonitrile: Crystallographic, Thermal, and DFT Study" in Crystal Growth & Design, 20, no. 5 (2020):3018-3033,
https://doi.org/10.1021/acs.cgd.9b01661 . .

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