Density, detonation property, and sensitivity may be the most valued features when evaluating an energetic material. By reasoning structure-property relationships, a nitro-free planar energetic material with high nitrogen and oxygen content, 7-hydroxy-difurazano[3,4-:3',4'-]furoxano[3″,4″-]azepine (), was synthesized using a unique and facile approach. The structure was fully characterized by IR and NMR spectra, elemental analysis, differential scanning calorimetry (DSC), and single-crystal X-ray diffraction. The expected properties of , including a high density of 1.92 g cm, high detonation velocity of 8,875 m s, and low mechanical sensitivities (impact sensitivity, 21 J and friction sensitivity, >360 N), confirm our strategy. Interestingly, the single-crystal structures of reveal expected face-to-face and edge-to-face π-interactions in the crystal stacking. The remarkable differences in crystal stacking of provide unequivocal evidence that face-to-face π-π interactions contribute significantly to closer assembly and higher density.