We rationalize these structural and electronic features using molecular orbital theory, showing that the topology of the singly occupied molecular orbital is uniquely suited to extend into exclusively bonding π-bands along the stacking direction. This type of multi-center interaction is reminiscent of so-called pancake bonds, where, however, equidistant stacking is typically avoided by Peierls (or Jahn-Teller) distortion. The reason for the unexpected absence of symmetry breaking in the (T → 0K) ground state of K3C6O6 is argued to be a combination of both inter-ring covalent bonding and large electrostatic repulsion. The P6/mmm phase of K3C6O6 would, if made, be among the most ionic pancake-bonded systems known. And despite being highly charged, the distance between rhodizonates anions calculates as 3.34 Å, much below the sum the van der Waals radii. Density of States near the Fermi level of K3C6O6 is predicted to be exceptionally high, almost on par with elemental Cu and possibly exceeding that of superconductors like MgB2 75 and high pressure SH3. This prediction is sensitive to the precise stacking distance, a parameter that will increase with temperature, leading us to expect a negative temperature coefficient of resistivity.