Novel complexes possessing Hg–(Cl, Br, I)⋯OC halogen bonding and unusual Hg2S2(Br/I)4 kernel. The usefulness of τ4′ structural parameter. (15th May 2018)

• Record Type: Journal Article
• Authors: Rosiak, Damian; Okuniewski, Andrzej; Chojnacki, Jarosław
• Is Part Of: Polyhedron. Volume 146(2018)
• Page Start: 35
• Page End: 41
• Publication Date: 2018-05-15
• Subjects: Halogen bond -- Benzoylthioureas -- Mercury complexes -- Bridging sulfur -- Metal cation-π interaction; Chemistry, Inorganic -- Periodicals; Chimie inorganique -- Périodiques; Organometaalverbindingen; Anorganische chemie; 546.05
• DOI: 10.1016/j.poly.2018.02.016
• Languages: English
• ISSNs: 0277-5387

Abstract

Graphical abstract: One mononuclear and two isostructural, binuclear Hg(II) complexes have been synthesized and characterized. Presented complexes comprise unique Hg-(Cl, Br, I)⋯OC interactions. The geometries of binuclear complexes are highly distorted with the alarmingly low value of τ 4 ′ parameter suggesting the presence of additional donor that turned out to be Hg⋯π interaction. Abstract: One mononuclear and two binuclear Hg II complexes have been synthesized and characterized by X-ray diffraction, ATR IR and Hirshfeld surface analysis. Single-crystal X-ray diffraction showed that binuclear compounds are centrosymmetric and isostructural. All complexes form bifurcated intermolecular N–H⋯O hydrogen bonds that contribute to a formation of the centrosymmetric dimers. In binuclear complexes, sulfur atoms of thiourea ligands take the bridging role. These are the first examples of such compounds with mercury. In binuclear complexes of group 12 elements, halogens are usually the bridging atoms. The geometries of binuclear complexes are highly distorted with alarmingly low value of τ 4 ′ parameter suggesting presence of additional donor that turned out to be phenyl ring (Hg⋯ π interaction). The crystal structures are stabilized by additional noncovalent interactions, including halogen bonding which leads to the formation of chains. The differences and similarities of these complexes indicate that halogen ions have a great impact on the structures. Presented complexes comprise unique interactions between mercury-bonded halogen atoms and neighboring oxygen atoms of carbonyl groups (Hg–(Cl, Br, I)⋯OC contacts).