Abstract
The intermolecular interactions in a series of new complexes Re(CO)3(N,N)X (N,N is a halogen substituted bidentate N–N donor and X is Cl or Br) have been studied crystallographically and computationally. Metal-bound halogens are more effective than carbon-bound halogens in forming significant intermolecular interactions.
Highlights
A series of ten rhenium tricarbonyl complexes (C1–C10), bearing halogen-substituted bidentate N,N-donor ligands with halogens or trifluoromethyl groups (X = –F, –contact and metal-bound halogen (Cl), –Br, and –CF3) in different positions on the aromatic rings were synthesized and characterized by FT-IR and 1H-NMR spectroscopy and their solid-state structures were determined by single crystal X-ray diffraction
Politzer et al showed the existence of an electropositive crown so-called “σ-hole” – a zone of low electron density displaying a positive electrostatic potential of the halogen atom directed to the electron donor.[13,14]
The crystal structure of all complexes comprises a molecule of rhenium complex in which a bidentate N,N-donor ligand, three carbonyl groups, in a facial arrangement, and an axial chloro or bromo group make up the coordination sphere of the Re center which exhibits a distorted octahedral geometry
Summary
Molecular chemistry[6] and crystal structure prediction.[7]. The competition between different types of non-covalent interactions in the solid-state and knowledge of the strengths of such interactions is at the heart of crystal engineering.[8]. This complex was synthesized by a procedure similar to C2, but using ligand L4 (0.55 mmol, 0.24 g) and ReIJCO)5Cl (0.55 mmol, 0.20 g). This complex was synthesized by a procedure similar to C2 but using ligand L5 and ReIJCO)5Cl (0.55 mmol, 0.20 g). The interaction energies were corrected for the basis set superposition error (BSSE) using the counterpoise method.[56] The molecular electrostatic potential (MEP) for each complex was done by the Gaussian[09] program with BP86-D3 function using def2-TZVP basis set (Fig. S17–S26†).[57] The non-covalent interaction index (NCI)[58] of the intramolecular interactions was obtained by direct Gaussian cube file to NCI routine via total electron. The similarities and dissimilarities between related crystal structures can be identified
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