Axial–equatorial isomerism and semiexperimental equilibrium structures of fluorocyclohexane

Abstract

An experimental-computational methodology combining rotational data, high-level ab initio calculations and predicate least-squares fitting is applied to the axial–equatorial isomerism and semiexperimental equilibrium structure determination of fluorocyclohexane. New supersonic-jet microwave measurements of the rotational spectra of the two molecular conformations, together with all ¹³C isotopologues of both isomeric forms are reported. Equilibrium rotational constants are obtained from the ground-state rotational constants corrected for vibration–rotation interactions and electronic contributions. Equilibrium structures were determined by the mixed estimation (ME) method. Different computational methods were tested for the evaluation of predicate values of the structural parameters, and a computationally effective procedure for estimating reliable dihedral angles is proposed. Structural parameters were fitted concurrently to predicate parameters and moments of inertia, affected with appropriate uncertainties. The new structures of the title compound are regarded as accurate to 0.001 Å and 0.2°, illustrating the advantages of this methodology. Structural comparisons are offered with the cyclohexane prototype, revealing subtle substituent effects. For comparison purposes the equilibrium structures for the two fluorocyclohexane isomers and cyclohexanone are computed from high-level ab initio theory with inclusion of adjustments for basis set dependence and correlation of the core electrons.