Λ-Cobalt(III) sepulchrate trinitrate crystallizes inP6322 withZ= 2 (Z′ = 1/6) at room temperature. Slabs perpendicular to the hexagonal axis comprise molecules Co(sepulchrate) alternating with nitrate groupsAandB. Coordinated by six sepulchrate molecules, highly disordered nitrate groupsCare accommodated between the slabs. Here we report the fully ordered, low-temperature crystal structure of Co(sep)(NO3)3. It is found to be a high-Z′ structure withZ′ = 12 of the 12-fold 6a_{h}\times\sqrt{3}b_{h}\times c_{h} superstructure with monoclinic symmetryP21(cunique). Correlations between structural parameters are effectively removed by refinements within the superspace approach. Superstructure formation is governed by a densification of the packing in conjunction with ordering of nitrate groupC, the latter assuming different orientations for each of theZ′ = 12 independent copies in the superstructure. The Co(sep) moiety exhibits small structural variations over its 12 independent copies, while orientations of nitrate groupsAandBvary less than the orientations of the nitrate groupCdo. Molecular packing in the superstructure is found to be determined by short C—H...H—C contacts, with H...H distances of 2.2–2.3 Å, and by short C—H...O contacts, with H...O distances down to 2.2 Å. These contacts presumably represent weak C—H...O hydrogen bonds, but in any case they prevent further densification of the structure and strengthening of weak N—H...O hydrogen bonds with observed H...O distances of 2.4–2.6 Å.