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ErCo2 is Cubic Laves structured and crystallizes in the cubic Fd-3m space group. The structure is three-dimensional. Er is bonded in a 12-coordinate geometry to twelve equivalent Co atoms. All Er–Co bond lengths are 2.95 Å. Co is bonded to six equivalent Er and six equivalent Co atoms to form a mixture of edge, face, and corner-sharing CoEr6Co6 cuboctahedra. All Co–Co bond lengths are 2.52 Å.
ErCo2(RhB2)2 crystallizes in the tetragonal P4_2mc space group. The structure is three-dimensional. Er3+ is bonded in a 12-coordinate geometry to twelve B3- atoms. There are a spread of Er–B bond distances ranging from 2.94–3.07 Å. Rh3+ is bonded to five B3- atoms to form distorted RhB5 trigonal bipyramids that share corners with four equivalent RhB5 trigonal bipyramids, corners with four equivalent CoB5 trigonal bipyramids, edges with two equivalent RhB5 trigonal bipyramids, and edges with four equivalent CoB5 trigonal bipyramids. There are three shorter (2.17 Å) and two longer (2.19 Å) Rh–B bond lengths. Co+1.50+ is bonded to five B3- atoms to form distorted CoB5 trigonal bipyramids that share corners with four equivalent RhB5 trigonal bipyramids, corners with four equivalent CoB5 trigonal bipyramids, edges with two equivalent CoB5 trigonal bipyramids, and edges with four equivalent RhB5 trigonal bipyramids. There are a spread of Co–B bond distances ranging from 2.09–2.19 Å. There are two inequivalent B3- sites. In the first B3- site, B3- is bonded in a 6-coordinate geometry to three equivalent Er3+, two equivalent Rh3+, three equivalent Co+1.50+, and one B3- atom. The B–B bond length is 1.71 Å. In the second B3- site, B3- is bonded in a 6-coordinate geometry to three equivalent Er3+, three equivalent Rh3+, two equivalent Co+1.50+, and one B3- atom. The B–B bond length is 1.91 Å.