M^II–Malonate Complexes (M = Mg, Cu, Ni and Co) Characterized by Layered Structures: Experimental Observation, Hirshfeld Surface Analysis and Theoretical Study

Abstract

A MgII complex containing malonate as the primary ligand and 4‐aminopyridine as the secondary ligand (counter ion), namely (ampyH)2[Mg(mal)2(H2O)2] (1; ampyH = protonated 4‐aminopyridine, malH2 = malonic acid), has been synthesized from purely aqueous media just by mixing the reactants in their stoichiometric proportions. Its crystal structure was determined by single‐crystal X‐ray diffraction. In 1, monomeric metal malonate units [Mg(mal)2(H2O)2]2– are interlinked through hydrogen bonds to generate infinite 2D supramolecular sheets. These supramolecular sheets are bridged by 4‐aminopyridine molecules to generate a 3D structure. Similar complexes containing 4‐aminopyridine as the secondary ligand (counter ion) show an identical self‐assembly process, except for the copper analogue, which was found to be polymeric in nature. By means of DFT theoretical calculations (BP86‐D3/def2‐TZVPD), we provide a plausible explanation for this different behaviour and present an energetic analysis of the complexes. The Hirshfeld surfaces of the Mg structure and related Cu, Ni and Co structures were analyzed to clarify the nature of the intermolecular interactions.

Newly synthesized homomultinuclear Co (II) and Cu (II) bissalamo‐like complexes: Structural characterizations, Hirshfeld analyses, fluorescence and antibacterial properties

“…The resulting 2D map corresponds to the O···H, C···H and H···H interactions between the Hirshfeld surface of complexes 1 and 2 . All fingerprint profiles are occupied by gray areas, and the blue color is indicated by its different short‐range interaction, as shown in Figure .…”

A new non-centrosymmetric microporous fluorinated iron phosphate: Structural elucidation, spectroscopic study and Hirshfeld surface analysis

“…The intermolecular interactions [31][32][33][37][38][39][40][41][42][43][44] in the crystal structure were quantified using Hirshfeld surface analysis and the associated 2D fingerprint plots [45][46][47] were calculated via the Crystal Explorer 3.0 [48] , which accepts a structure input file in the CIF format. This approach has been built on the electron distribution calculated as the sum of spherical atom electron densities [49,50] .…”

Experimental and Computational Study of Counterintuitive ClO4–···ClO4– Interactions and the Interplay between π+–π and Anion···π+ Interactions

“…Both experimental and theoretical evidence of interesting synergetic effects between anion-π and HB and between anion-π and π−π stacking interactions has been reported recently which displays that the interplay between these interactions can direct to strong cooperativity effects. [29][30][31][32][33][34][35][36][37][38][39][40] Recently, experimental evidence of anion-π-π interactions has emerged from crystallographic studies [41][42][43][44] on synthesized compounds based on the electron-deficient pyridine moieties, suggesting the possibility to enhance anion-π binding by π-π stacking. In the present study, we investigate and explore the structural features of this anion-π-π complex, and the energetic associated to anion-π, π + -π + and π + -π interactions using a combination of single crystal X-ray diffraction and density 3 functional theory (DFT) calculations.…”