ACS Publications. Most Trusted. Most Cited. Most Read
My Activity
CONTENT TYPES

Figure 1Loading Img

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

Cite this: Cryst. Growth Des. 2020, 20, 5, 3018–3033
Publication Date (Web):March 30, 2020
https://doi.org/10.1021/acs.cgd.9b01661
Copyright © 2020 American Chemical Society

    Article Views

    402

    Altmetric

    -

    Citations

    LEARN ABOUT THESE METRICS
    Other access options
    Supporting Info (1)»

    Abstract

    Abstract Image

    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.

    Read this article

    To access this article, please review the available access options below.

    Get instant access

    Purchase Access

    Read this article for 48 hours. Check out below using your ACS ID or as a guest.

    Recommended

    Access through Your Institution

    You may have access to this article through your institution.

    Your institution does not have access to this content. You can change your affiliated institution below.

    Supporting Information

    ARTICLE SECTIONS
    Jump To

    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.cgd.9b01661.

    • TGA curves, XRPD diffractograms, IR data, structural parameters, computational results, optical and SEM images, and NMR spectra (PDF)

    Accession Codes

    CCDC 19669121966913 contain the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif, or by emailing [email protected], or by contacting The Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336033.

    Terms & Conditions

    Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system: http://pubs.acs.org/page/copyright/permissions.html.

    Cited By

    This article is cited by 3 publications.

    1. Jovana Araskov, Predrag Ristic, Aleksandar Visnjevac, Andrej Milivojac, Dragana Mitic, Nenad Filipovic, Tamara Todorovic. Zn(II) complex with pyridine based 1,3-selenazolyl-hydrazone: Synthesis, structural characterization and DFT study. Journal of the Serbian Chemical Society 2023, 88 (12) , 1355-1367. https://doi.org/10.2298/JSC230831079A
    2. Xinli Leng, Wei Li, Xiaoqing Liu, Li Wang. Direct observation of meta-selective C-H activation on Pd(1 1 1) by scanning tunneling microscopy. Chemical Physics 2020, 539 , 110981. https://doi.org/10.1016/j.chemphys.2020.110981
    3. J. Prakasha Reddy. Crystal structure and Hirshfeld surface analysis of dichlorido(methanol-κ O )bis(2-methylpyridine-κ N )copper(II). Acta Crystallographica Section E Crystallographic Communications 2020, 76 (11) , 1771-1774. https://doi.org/10.1107/S2056989020014036

    Pair your accounts.

    Export articles to Mendeley

    Get article recommendations from ACS based on references in your Mendeley library.

    Pair your accounts.

    Export articles to Mendeley

    Get article recommendations from ACS based on references in your Mendeley library.

    You’ve supercharged your research process with ACS and Mendeley!

    STEP 1:
    Click to create an ACS ID

    Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

    Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

    Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

    MENDELEY PAIRING EXPIRED
    Your Mendeley pairing has expired. Please reconnect