Hydrogen bond networks in five- and eight-membered palladium and platinum complexes derived from bis(2-aminophenyl)ether and bis(2-aminophenyl)thioether ligands Uvaldo Hernández-Balderas a , Noemí Andrade-López a,⇑ , José G. Alvarado-Rodríguez a , Rafael Moreno-Esparza b , Margarita Paneque c a Centro de Investigaciones Químicas, Universidad Autónoma del Estado de Hidalgo, Ciudad Universitaria, Carretera Pachuca–Tulancingo km 4.5, Colonia Carboneras, Mineral de la Reforma, Hgo. C.P. 42184, Mexico b Facultad de Química (UNAM), Ed. B. Ave. Universidad 3000, C.P. 04510, Coyoacán, México D.F., Mexico c Instituto de Investigaciones Químicas (IIQ) and Departamento de Química Inorgánica, CSIC and Universidad de Sevilla, Av. Américo Vespucio 49, 41092 Sevilla, Spain article info Article history: Received 24 October 2014 Accepted 6 February 2015 Available online 14 February 2015 Keywords: Nitrogenate ligands Pd and Pt complexes X-ray diffraction j 2 N, jNjS, and j 2 NjS modes Noncovalent interactions abstract The reaction of [M II (MeCN) 2 Cl 2 ](M = Pd, Pt) with the diamino ligands either bis(2-aminophenyl)ether or bis(2-aminophenyl)thioether {(NH 2 -C 6 H 4 ) 2 D}[D =O(L 1 ); D =S(L 2 )] yielded neutral coordination com- plexes of general formulae [M(L n )Cl 2 ][M = Pd, n =1(1); Pt, n =1(2); Pd, n =2(3); Pd, n =2(4); Pt, n =2(5). The reaction of L 2 with K 2 [PtCl 6 ] promoted the mono-deprotonation of the diamino ligand to yield the neutral complex [Pt IV {(NH 2 -C 6 H 4 )S(NH-C 6 H 4 )}Cl 3 ](6); when the H 2 [PtCl 6 ] acid was used an ion- ic complex [Pt IV (L 2 )Cl 3 ]Cl (7) was obtained. All complexes were characterized by NMR in solution, vibra- tional spectroscopy, and by X-ray diffraction studies. The molecular structures of the complexes revealed different coordination patterns of the diamino ligands; L 1 just displayed a j 2 N mode meanwhile L 2 exhib- ited a wide variety of patterns (j 2 N, jNjS, and j 2 NjS) forming chelate rings of five- or eight-members. The presence of N–H functions in the ligand moieties enhanced the formation of extended hydrogen- bond networks; these supramolecular arrangements were mainly discussed at unitary and binary levels and sorted according to the molecular coordination patterns observed. Ó 2015 Elsevier Ltd. All rights reserved. 1. Introduction In Coordination Chemistry, nitrogenate ligands based on the chemical framework I have been utilized as precursors of transi- tional metal complexes of Ti II , Zr II , Zr IV , Hf II , Hf IV , [1] Co II , and Fe II [2]. A number of these complexes have displayed catalytic applica- tions in asymmetric synthesis and in alkene polymerization; this catalytic behavior has been associated with the flexibility of the molecular framework and with the nature of the donor atom pre- sent in the ligands [2–4]. From a structural point of view, a thor- ough analysis of a number of structures of complexes containing ligands based on the framework I, retrieved from the Cambridge Structural Database (version 5.35, updated February 2014), revealed that, in most of the ligands of the type I used, the atoms attached to the nitrogen atoms are organic groups such as substi- tuted phenyl groups or tert-butyl groups in order to take advantage of their electronic and steric inherent effects. Nevertheless, the increase of these organic groups led to a concomitant decrease in the number of hydrogen atoms attached to the nitrogen atoms, reducing the ability of the molecular complexes, for example, to display N–H–acceptor interactions. In this regard, it is widely rec- ognized that noncovalent interactions such as hydrogen- and halo- gen bonding play a fundamental role in the formation of supramolecular aggregates that display fascinating architectures achieved in solid state [5–8]. In particular, it has been highlighted the importance of the presence of N–H functions in platinum com- plexes; the presence of N–H–acceptor interactions may have a remarkable influence in the way that some platinum-based drugs select the DNA as a target in the cell [9]. Continuing with our studies of Coordination Chemistry of nitro- genate ligands with Group 10 metals [10–12] we thought worth- while to investigate the influence of the donor atom D in the coordination mode of the ligands L 1 and L 2 toward palladium and platinum and the role of the N–H groups in the formation of supramolecular arrangements. To the best of our knowledge, there is just one report of the coordination studies of these ligands, in particular L 1 , with Zn II ; [13] in this report the analysis of the http://dx.doi.org/10.1016/j.poly.2015.02.004 0277-5387/Ó 2015 Elsevier Ltd. All rights reserved. ⇑ Corresponding author. E-mail address: nandrade@uaeh.edu.mx (N. Andrade-López). Polyhedron 90 (2015) 165–174 Contents lists available at ScienceDirect Polyhedron journal homepage: www.elsevier.com/locate/poly