The remarkable effect that secondary bonding interactions can have on the macroscopic properties of a material is illustrated by two polymorphs of the title compound. The phase which is most stable under ambient pressure and temperature consists of puckered supramolecular ribbon polymers assembled by Te-N secondary bonding interactions and displays a characteristic red-orange color. A second yellow phase consists of ribbons with alternating short and long intermolecular Te-N secondary bonding distances and is metastable; at 127 degrees C the material undergoes an exothermic irreversible transition to the red polymorph. A third phase consists of pyridine-solvated supramolecular dimers; it is also yellow and transforms into the red phase after the crystals effloresce. Computational DFT studies indicate that the observed changes in optical properties are related to intermolecular mixing pi orbitals enabled by the supramolecular interactions and the symmetry of the supramolecular synthon.