Diverse Self-Assembled Molecular Architectures Promoted by C–H···O and C–H···Cl Hydrogen Bonds in a Triad of α-Diketone, α-Ketoimine, and an Imidorhenium Complex: A Unified Analysis Based on XRD, NEDA, SAPT, QTAIM, and IBSI Studies

Abstract

X-ray structural elucidation, supramolecular self-assembly, and energetics of existential noncovalent interactions for a triad comprising α-diketone, α-ketoimine, and an imidorhenium complex are highlighted in this report. Molecular packing reveals a self-assembled 2D network stabilized by the C–H···O H-bonds for the α-diketone (benzil), and the first structural report of Brown and Sadanaga stressing on the prevalence of only the van der Waals forces seems to be an oversimplified conjecture. In the α-ketoimine, the imine nitrogen atom undergoes intramolecular N···H interaction to render itself inert toward intermolecular C–H···N interaction and exhibits two types of C–H···O H-bonds in consequence to generate a self-assembled 2D molecular architecture. The imidorhenium complex features a self-aggregated 3D packing engendered by the interplay of C–H···Cl H-bonds along with the ancillary C–H···π, C···C, and C···Cl contacts. To the best of our knowledge, in rhenium chemistry, this imidorhenium complex unravels the first example of self-associated 3D molecular packing constructed by the directional hydrogen bonds of C–H···Cl type. The presence of characteristic supramolecular synthons, viz., R₂²(12), R₂²(16), and R₂²(14), in the α-diketone, α-ketoimine, and imidorhenium complex, respectively, has prompted us to delve into the energetics of noncovalent interactions. Symmetry-adapted perturbation theory analysis has authenticated a stability order: R₂²(14) > R₂²(12) > R₂²(16) based on the interaction energy values of −25.97, −9.93, and −4.98 kcal/mol, respectively. The respective average contributions of the long-range dispersion, electrostatic, and induction forces are 58.5, 32.8, and 8.7%, respectively, for the intermolecular C–H···O interactions. The C–H···Cl interactions experience comparable contribution from the dispersion force (57.9% on average), although the electrostatic and induction forces contribute much less, 28.0 and 14.1%, respectively, on average. The natural energy decomposition analysis has further attested that the short-range, interfragment charge transfer occurring via the lp(O/Cl) → σ*(C–H) routes contributes 17–25% of the total attractive force for the C–H···O and C–H···Cl interactions. Quantum theory of atoms in molecules analysis unfolds a first-order exponential decay relation (y = 8.1043e^–x/0.4095) between the electron density at the bond critical point and the distance of noncovalent interactions. The distances of noncovalent interactions in the lattices are internally governed by the individual packing patterns rather than the chemical nature of the H-bond donors and acceptors. Intrinsic bond strength index analysis shows promise to correlate the electron density at BCP with the SAPT-derived interaction energy for the noncovalent interactions. Two factors: (i) nearly half the HOMO–LUMO energy difference for the imidorhenium complex (∼30 kcal/mol) compared to the organics, and (ii) ∼60% localization of HOMO over the mer-ReCl₃ moiety clearly indicate an enhanced polarizability of the complex facilitating the growth of weak C–H···Cl H-bonds.