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
Samo za registrovane korisnike
2020
Autori
Ristić, PredragBlagojević, Vladimir A.
Janjić, Goran V.
Rodić, Marko
Vulić, Predrag J.
Donnard, Morgan
Gulea, Mihaela
Chylewska, Agnieszka
Makowski, Mariusz
Todorović, Tamara
Filipović, Nenad R.
Članak u časopisu (Objavljena verzija)
Metapodaci
Prikaz svih podataka o dokumentuApstrakt
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.
Ključne reči:
metals / ligands / Pt complexes / Pd complexes / molecular interactions / molecular structure / crystal structureIzvor:
Crystal Growth & Design, 2020, 20, 5, 3018-3033Izdavač:
- American Chemical Society
Finansiranje / projekti:
- Usmerena sinteza, struktura i svojstva multifunkcionalnih materijala (RS-MESTD-Basic Research (BR or ON)-172057)
Napomena:
- Supplementary material: https://hdl.handle.net/21.15107/rcub_dais_9455
- Peer-reviewed manuscript: https://hdl.handle.net/21.15107/rcub_dais_9454
Povezane informacije:
- Druga verzija
https://hdl.handle.net/21.15107/rcub_dais_9454 - Povezani sadržaj
https://hdl.handle.net/21.15107/rcub_dais_9455
DOI: 10.1021/acs.cgd.9b01661
ISSN: 1528-7483
WoS: 000535174000024
Scopus: 2-s2.0-85089237632
Institucija/grupa
Институт техничких наука САНУ / Institute of Technical Sciences of SASATY - JOUR AU - Ristić, Predrag AU - Blagojević, Vladimir A. AU - Janjić, Goran V. 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 R. PY - 2020 UR - https://dais.sanu.ac.rs/123456789/9453 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 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 SP - 3018 EP - 3033 VL - 20 IS - 5 DO - 10.1021/acs.cgd.9b01661 UR - https://hdl.handle.net/21.15107/rcub_dais_9453 ER -
@article{ author = "Ristić, Predrag and Blagojević, Vladimir A. and Janjić, Goran V. 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 R.", 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", 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 = "3018-3033", volume = "20", number = "5", doi = "10.1021/acs.cgd.9b01661", url = "https://hdl.handle.net/21.15107/rcub_dais_9453" }
Ristić, P., Blagojević, V. A., Janjić, G. V., Rodić, M., Vulić, P. J., Donnard, M., Gulea, M., Chylewska, A., Makowski, M., Todorović, T.,& Filipović, N. R.. (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., 20(5), 3018-3033. https://doi.org/10.1021/acs.cgd.9b01661 https://hdl.handle.net/21.15107/rcub_dais_9453
Ristić P, Blagojević VA, Janjić GV, Rodić M, Vulić PJ, Donnard M, Gulea M, Chylewska A, Makowski M, Todorović T, Filipović NR. 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 https://hdl.handle.net/21.15107/rcub_dais_9453 .
Ristić, Predrag, Blagojević, Vladimir A., Janjić, Goran V., Rodić, Marko, Vulić, Predrag J., Donnard, Morgan, Gulea, Mihaela, Chylewska, Agnieszka, Makowski, Mariusz, Todorović, Tamara, Filipović, Nenad R., "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 ., https://hdl.handle.net/21.15107/rcub_dais_9453 .