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CoBr2 is trigonal omega structured and crystallizes in the trigonal P-3m1 space group. The structure is two-dimensional and consists of one CoBr2 sheet oriented in the (0, 0, 1) direction. Co2+ is bonded to six equivalent Br1- atoms to form edge-sharing CoBr6 octahedra. All Co–Br bond lengths are 2.59 Å. Br1- is bonded in a distorted T-shaped geometry to three equivalent Co2+ atoms.
CoN5Br2NO2 crystallizes in the monoclinic C2/c space group. The structure is one-dimensional and consists of four nitrous acid molecules and two CoN5Br2 ribbons oriented in the (0, 0, 1) direction. In each CoN5Br2 ribbon, Co4+ is bonded in a trigonal bipyramidal geometry to five N+1.67- atoms. There are a spread of Co–N bond distances ranging from 1.56–1.98 Å. There are three inequivalent N+1.67- sites. In the first N+1.67- site, N+1.67- is bonded in a single-bond geometry to one Co4+ atom. In the second N+1.67- site, N+1.67- is bonded in a 1-coordinate geometry to one Co4+ and one Br5+ atom. The N–Br bond length is 1.83 Å. In the third N+1.67- site, N+1.67- is bonded in a 1-coordinate geometry to one Co4+ and one Br5+ atom. The N–Br bond length is 1.82 Å. Br5+ is bonded in a water-like geometry to two N+1.67- atoms.
CoN5Br2NO2 crystallizes in the monoclinic C2/c space group. The structure is one-dimensional and consists of four nitrous acid molecules and two CoN5Br2 ribbons oriented in the (0, 0, 1) direction. In each CoN5Br2 ribbon, Co4+ is bonded in a trigonal bipyramidal geometry to five N+1.67- atoms. There are a spread of Co–N bond distances ranging from 1.56–1.99 Å. There are three inequivalent N+1.67- sites. In the first N+1.67- site, N+1.67- is bonded in a single-bond geometry to one Co4+ atom. In the second N+1.67- site, N+1.67- is bonded in a 1-coordinate geometry to one Co4+ and one Br5+ atom. The N–Br bond length is 1.83 Å. In the third N+1.67- site, N+1.67- is bonded in a 1-coordinate geometry to one Co4+ and one Br5+ atom. The N–Br bond length is 1.82 Å. Br5+ is bonded in a water-like geometry to two N+1.67- atoms.