The Z′ = 12 superstructure of Λ-cobalt(III) sepulchrate trinitrate governed by C—H⋯O hydrogen bonds

Λ-Cobalt(III) sepulchrate trinitrate crystallizes in P6(3)22 with Z = 2 (Z′ = 1/6) at room temperature. Slabs perpendicular to the hexagonal axis comprise molecules Co(sepulchrate) alternating with nitrate groups A and B. Coordinated by six sepulchrate molecules, highly disordered nitrate groups C are accommodated between the slabs. Here we report the fully ordered, low-temperature crystal structure of Co(sep)(NO(3))(3). It is found to be a high-Z′ structure with Z′ = 12 of the 12-fold [Image: see text] superstructure with monoclinic symmetry P2(1) (c unique). 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 group C, the latter assuming different orientations for each of the Z′ = 12 independent copies in the superstructure. The Co(sep) moiety exhibits small structural variations over its 12 independent copies, while orientations of nitrate groups A and B vary less than the orientations of the nitrate group C do. 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.