Treatment of the [AuCl(tetrahydrothiophene)] complex with 4-chloro-2-iodo-1-isocyanobenzene furnished the gold(I) compound [AuCl(CNC6H3-4-Cl-2-I)] (1). In the crystal structure of 1, the linear C–Au–Cl group is subject to the solid-state head-to-tail pairing which is determined by the aurophilic Au···Au and the rare π-holeCN···Cl interactions. These two types of structure-determining interactions are complementary to each other and the system of Au···Au and CCN···Cl contacts accomplishes 2D extended ladder-type architecture. In addition, the terminal I-atoms are involved in the three-center halogen bonding. Density functional theory calculations, employing a set of computational tools, verified the role of Au···Au and π-holeCN···Cl noncovalent bonds in the spectrum of noncovalent forces.

Two new Mn(II) and Zn(II) metal-organic compounds of 1,10-phenanthroline and methyl benzoates viz. [Mn(phen)2Cl2]2-ClBzH (1) and [Zn(4-MeBz)2(2-AmPy)2] (2) (where, 4-MeBz = 4-methylbenzoate, 2-AmPy = 2-aminopyridine, phen = 1,10-phenanthroline, 2-ClBzH = 2-chlorobenzoic acid) have been synthesized and characterized using elemental analysis, TGA, spectroscopic (FTIR, electronic) and single crystal X-ray diffraction techniques. Crystal structure analysis of the compounds reveals the presence of various non-covalent interactions which provides stability to the crystal structures. Crystal structure analysis of the compound 1 reveals the formation of supramolecular dimer of 2-ClBzH enclathrated within the hexameric host cavity formed by the neighboring monomeric units. Compound 2 is a mononuclear compound of Zn(II) where flexible binding topologies of 4-CH3Bz is observed with the metal centre. Moreover various non-covalent interactions such as lp(O)-π, lp(Cl)-π, C‒H∙∙∙Cl, π-stacking interactions as well as N‒H∙∙∙O, C‒H∙∙∙O and C‒H∙∙∙π hydrogen bonding interactions are found to be involved in plateauing the molecular self-association of the compounds. The remarkable enclathration of the H-bonded 2-ClBzH dimer into a supramolecular cavity formed by two [Mn(phen)2Cl2] complexes has been further studied theoretically using density functional theory (DFT) calculations, non-covalent interaction (NCI) plot index and quantum theory of atoms in molecules (QTAIM) computational tools. Synergistic effects have been also analysed using molecular electrostatic potential (MEP) surface analysis.

Herein, we have reported the synthesis and characterization [single crystal X-ray diffraction technique, spectroscopic etc.] of two new Ni(II) and Zn(II) coordination compounds viz. [Ni(2,6-PDC)2]2[Ni(en)2(H2O)2]2[Ni(en)(H2O)4]·4H2O (1) and [Zn(2,6-PDC)(Hdmpz)2] (2) (where, 2,6-PDC = 2,6-pyridinedicarboxylate, en = ethylene-1,2-diamine, Hdmpz = 3,5-dimethyl pyrazole). Compound 1 is found to crystallize as a multicomponent Ni(II) compound with five discrete complex moieties; whereas, compound 2 is a mononuclear compound of Zn(II). Deep analysis of the crystal structure of compound 1 unfolds unusual dual enclathration of guest complex cationic moieties within the supramolecular host cavity stabilized by anion‒π, π-stacking, N‒H⋯O, C‒H⋯O and O‒H⋯O hydrogen bonding interactions. Interestingly, further enclathration of a complex cationic moiety is observed within another supramolecular host cavity formed involving anionic complex moieties and lattice water molecules in 1. Again, the crystal structure of compound 2 is stabilized by the presence of unconventional C‒H⋯π(chelate ring) interactions along with C‒H⋯O, C‒H⋯N hydrogen bonding, π-stacking, C‒H⋯π(pyridyl) interactions. These non-covalent interactions have been further studied theoretically using density functional theory (DFT) calculations, molecular electrostatic potential (MEP) surfaces, non-covalent interaction (NCI) plot index and quantum theory of atoms in molecules (QTAIM) computational tools. The computational study displays that π-stacking or H-bonds greatly tune the directionality of compound 1 although non-directional electrostatic forces dominate energetically. For compound 2, combined QTAIM/NCI plot analysis confirms the presence of unconventional C‒H⋯π(chelate ring) interaction along with other weak interactions obtained from the crystal structure analysis. Further, the individual energy contributions of these weak yet significant non-covalent interactions have also been determined computationally.