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
2020
Аутори
Ristić, PredragBlagojević, Vladimir
Janjić, Goran
Rodić, Marko
Vulić, Predrag
Donnard, Morgan
Gulea, Mihaela
Chylewska, Agnieszka
Makowski, Mariusz
Todorović, Tamara
Filipović, Nenad
Чланак у часопису (Рецензирана верзија)
Метаподаци
Приказ свих података о документуАпстракт
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.
Кључне речи:
Metals / Ligands / Crystal structure / Molecular structure / Molecular interactions / Pt(II) / Pd(II) / M–S bond / DFT / C–H/M interactions / C–H/S interactions / C–H/Cl interactionsИзвор:
Crystal Growth & Design, 2020, 20, 5, 3018-3033Издавач:
- American Chemical Society (ACS)
Финансирање / пројекти:
- Усмерена синтеза, структура и својства мултифункционалних материјала (RS-MESTD-Basic Research (BR or ON)-172057)
Напомена:
- This is the peer-reviewed version of the article: Predrag Ristić, Vladimir Blagojević, Goran Janjić, Marko Rodić, Predrag Vulić, Morgan Donnard, Mihaela Gulea, Agnieszka Chylewska, Mariusz Makowski, Tamara Todorović, Nenad Filipović, 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, Cryst. Growth Des. 2020, 20, 5, 3018–3033, DOI: https://doi.org/10.1021/acs.cgd.9b01661
- The published version: https://cer.ihtm.bg.ac.rs/handle/123456789/4028
DOI: 10.1021/acs.cgd.9b01661
ISSN: 1528-7483; 1528-7505
WoS: 000535174000024
Scopus: 2-s2.0-85089237632
Институција/група
IHTMTY - JOUR AU - Ristić, Predrag AU - Blagojević, Vladimir AU - Janjić, Goran AU - Rodić, Marko AU - Vulić, Predrag AU - Donnard, Morgan AU - Gulea, Mihaela AU - Chylewska, Agnieszka AU - Makowski, Mariusz AU - Todorović, Tamara AU - Filipović, Nenad PY - 2020 UR - https://cer.ihtm.bg.ac.rs/handle/123456789/4029 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 - American Chemical Society (ACS) 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 VL - 20 IS - 5 SP - 3018 EP - 3033 DO - 10.1021/acs.cgd.9b01661 ER -
@article{ author = "Ristić, Predrag and Blagojević, Vladimir and Janjić, Goran and Rodić, Marko and Vulić, Predrag 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 = "American Chemical Society (ACS)", 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", volume = "20", number = "5", pages = "3018-3033", doi = "10.1021/acs.cgd.9b01661" }
Ristić, P., Blagojević, V., Janjić, G., Rodić, M., Vulić, P., 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 American Chemical Society (ACS)., 20(5), 3018-3033. https://doi.org/10.1021/acs.cgd.9b01661
Ristić P, Blagojević V, Janjić G, Rodić M, Vulić P, 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, Janjić, Goran, Rodić, Marko, Vulić, Predrag, 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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