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π–π Interactions in diimine Pt(II) complexes with thiacrown ligands: The crystal structure of (1,4,7-trithiacyclononane)(3,4,7,8-tetramethyl-1, 10-phenanthroline)platinum(II) hexafluorophosphate

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We wish to report the crystal structure for the heteroleptic platinum(II) complex with the crown thioether 1,4,7-trithiacyclononane (9S3) and the diimine ligand 3,4,7,8-tetramethyl-1,10-phenanthroline (tmphen), [Pt(9S3)(tmphen)](PF6)2 (1). The Pt(II) center is surrounded by a cis-S2N2 ligand environment formed by the bidentate diimine and two of the three sulfur atoms from the 9S3 ligand. These two sulfurs are positioned 2.2665(10) and 2.2612(11) Å from the Pt(II), but the third sulfur shows a long distance interaction at 2.8849(13) Å to form an elongated square pyramidal structure. An examination of the structure reveals π–π-intermolecular stacking of the phen groups with alternating distances of 3.53 and 3.62 Å between the planes of the phen ligands. A detailed survey of 12 other divalent Pt(II) and Pd(II) diimine complexes of 9S3 reveals three different stacking motifs involving π–π interactions in the solid state. Crystal Data for (1): P-1, a = 10.868(2) Å, b = 11.292(2) Å, c = 11.513(2) Å, α = 93.76(3)°, β = 90.82(3)°, γ = 92.28(3)°, V = 1408.5(5) Å3, Z = 2.

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Notes

  1. While the anions are the same for this series of cation structures, the data collection temperatures for the structures in this series varies considerably (150–303 K), precluding a more detailed comparison of π–π interaction distances.

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Acknowledgments

This research was generously supported by grants from the Petroleum Research Fund, administered by the American Chemical Society, the Grote Chemistry Fund at the University of Tennessee at Chattanooga, the Wheeler Odor Center at the University of Tennessee at Chattanooga and by the National Science Foundation, Research at Undergraduate Institutions Program.

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Authors and Affiliations

  1. Department of Chemistry, The University of Tennessee at Chattanooga, Chattanooga, Tennessee, U.S.

    Daron E. Janzen, Kentankumar Patel & Gregory J. Grant

  2. Department of Chemistry, Clemson University, Clemson,, South Carolina, U.S.

    Donald G. VanDerveer

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  1. Daron E. Janzen
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  2. Kentankumar Patel
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  3. Donald G. VanDerveer
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  4. Gregory J. Grant
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Correspondence to Gregory J. Grant.

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Crystallographic data for the structure reported in this paper have been deposited with the Cambridge Crystallographic Data Centre as CCDC 267337. Copies of the data can be obtained free of charge on application to CCDC, 12 Union Road, Cambridge, CB2 1 EZ UK (Fax: +44-1223-336-033); E-MAIL: deposit@ccdc.cam.ac.uk.

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Janzen, D.E., Patel, K., VanDerveer, D.G. et al. π–π Interactions in diimine Pt(II) complexes with thiacrown ligands: The crystal structure of (1,4,7-trithiacyclononane)(3,4,7,8-tetramethyl-1, 10-phenanthroline)platinum(II) hexafluorophosphate. J Chem Crystallogr 36, 83–91 (2006). https://doi.org/10.1007/s10870-005-9002-3

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