The synthesis and characterisation of a large family of hexametallic [Mn^III₆] Single-Molecule Magnets of general formula [Mn^III₆O₂(R-sao)₆(X)₂(sol)_4–6] (where R = H, Me, Et; X = ⁻O₂CR′ (R′ = H, Me, Ph etc) or Hal⁻; sol = EtOH, MeOH and/or H₂O) are presented. We show how deliberate structural distortions of the [Mn₃O] trinuclear moieties within the [Mn₆] complexes are used to tune their magnetic properties. These findings highlight a qualitative magneto-structural correlation whereby the type (anti- or ferromagnetic) of each Mn₂ pairwise magnetic exchange is dominated by the magnitude of each individual Mn-N-O-Mn torsion angle. The observation of magneto-structural correlations on such large polymetallic complexes is rare and represents one of the largest studies of this kind.