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

Predrag Ristić , Vladimir Blagojević , Goran Janjić , Marko Rodić , Predrag Vulić , Morgan Donnard , Mihaela Gulea , Agnieszka Chylewska , Mariusz Makowski , Tamara Todorović , Nenad Filipović


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.
Author Predrag Ristić
Predrag Ristić,,
, Vladimir Blagojević
Vladimir Blagojević,,
, Goran Janjić
Goran Janjić,,
, Marko Rodić
Marko Rodić,,
, Predrag Vulić
Predrag Vulić,,
, Morgan Donnard
Morgan Donnard,,
, Mihaela Gulea
Mihaela Gulea,,
, Agnieszka Chylewska (FCh / KChBionieorg. / LII)
Agnieszka Chylewska,,
- Laboratory of Intermolecular Interactions
, Mariusz Makowski (FCh / KChBionieorg. / LII)
Mariusz Makowski,,
- Laboratory of Intermolecular Interactions
, Tamara Todorović
Tamara Todorović,,
et al.`
Journal seriesCrystal Growth & Design, ISSN 1528-7483, e-ISSN 1528-7505, (N/A 100 pkt)
Issue year2020
Publication size in sheets0.75
ASJC Classification1600 General Chemistry; 2500 General Materials Science; 3104 Condensed Matter Physics
Languageen angielski
Score (nominal)100
Score sourcejournalList
ScoreMinisterial score = 100.0, 13-05-2020, ArticleFromJournal
Publication indicators Scopus SNIP (Source Normalised Impact per Paper): 2018 = 1.107; WoS Impact Factor: 2018 = 4.153 (2) - 2018=3.893 (5)
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