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Palladium(II) halide complexes of N,N,S-tridentate Schiff bases: synthesis, structural studies in solution and solid state, and analysis of Hirshfeld surfaces

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Abstract

The synthesis and characterization of bromo- and iodo complexes of Pd(II) containing tridentate anionic Schiff bases, derived from the ring-opening of 2-R-2-(2-pyridyl)benzothiazoline precursors (R = H, 1; R = Me, 2; R = C6H5, 3; R = C5H4N, 4) is described. The [Pd(Ln)X] complexes [for X = Br: n = 1 (1a), n = 2 (2a), n = 3 (3a), and n = 4, (4a); for X = I: n = 1 (1b), n = 2 (2b), n = 3 (3b), and n = 4 (4b)] were characterized in solution and in solid state by NMR and IR spectroscopy and by elemental analyses. In all complexes, the corresponding anionic Schiff ligand {Ln}− displayed a κ2NκS-tridentate coordination mode. X-ray diffraction studies of [Pd(L3)Br] (3a), [Pd(L3)I] (3b), [Pd(L4)Br] (4a), and [Pd(L4)I] (4b) complexes showed the formation of two five-membered chelate rings, with a distorted square planar geometry around the Pd(II) cation. Crystal structures of 3a, 3b, 4a, and 4b are stabilized by non-classical C–H···π, C–H···S, and C–H···X hydrogen bonding. The Hirshfeld surface analysis showed that the H···H contacts are predominant, and the C–H···S or C–H···π interactions were the major contributions in the stacking of the molecular complexes.

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Acknowledgements

JAAH and OMG be grateful to CONAHCYT México for their scholarships. This research was supported by project UAEH/DI/ICBI/Quí-12.

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Authors and Affiliations

  1. Área Académica de Química, Universidad Autónoma del Estado de Hidalgo, Ciudad Universitaria, Carretera Pachuca–Tulancingo km 4.5. Colonia Carboneras, C.P. 42184, Mineral de la Reforma, Hgo, Mexico

    Jesús-Alberto Alvarez-Hernández, Noemí Andrade-López, José G. Alvarado-Rodríguez, Oscar Muñoz-Granados & Gloria Sánchez-Cabrera

  2. Centro Conjunto de Investigación en Química Sustentable UAEM-UNAM, Unidad San Cayetano, Km 14.5 Carretera Toluca-Atlacomulco, C.P. 50200, Toluca, Edo. de Mexico, Mexico

    Diego Martínez-Otero

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Contributions

JAA-H contributed to the methodology and supporting, NA-L contributed to conceptualization, methodology, formal analysis, writing- original draft, writing-review and editing, supervision, resources, JGA-R contributed to formal analysis, writing-review & editing resources, OM-G contributed to the methodology and supporting, GS-C was involved in supporting and formal analysis, DM-O was involved in the formal analysis and data curation. All authors reviewed the manuscript

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Correspondence to Noemí Andrade-López.

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11243_2024_580_MOESM1_ESM.docx

CCDC 2305457 (3a, 100 K), 2305455 (3a’, 300 K), 2305456 (3b, 100 K), 2305459 (3b', 300 K), 2305454 (4a, 100 K), and 2305458 (4b, 100 K) contains the supplementary crystallographic data. These data can be obtained free of charge via http://www.ccdc.cam.ac.uk/conts/retrieving.html, or from the Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: (+44) -336-033; or e-mail: deposit@ccdc.cam.ac.uk.

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Alvarez-Hernández, JA., Andrade-López, N., Alvarado-Rodríguez, J.G. et al. Palladium(II) halide complexes of N,N,S-tridentate Schiff bases: synthesis, structural studies in solution and solid state, and analysis of Hirshfeld surfaces. Transit Met Chem (2024). https://doi.org/10.1007/s11243-024-00580-z

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