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PrB6 is Calcium hexaboride structured and crystallizes in the cubic Pm-3m space group. The structure is three-dimensional. Pr is bonded in a 1-coordinate geometry to twenty-four equivalent B atoms. All Pr–B bond lengths are 3.05 Å. B is bonded in a 1-coordinate geometry to four equivalent Pr and five equivalent B atoms. There is one shorter (1.66 Å) and four longer (1.76 Å) B–B bond length.
PRb is Halite, Rock Salt structured and crystallizes in the monoclinic C2/m space group. The structure is three-dimensional. Rb1+ is bonded to six equivalent P1- atoms to form a mixture of edge and corner-sharing RbP6 octahedra. The corner-sharing octahedral tilt angles are 0°. All Rb–P bond lengths are 3.53 Å. P1- is bonded to six equivalent Rb1+ atoms to form a mixture of edge and corner-sharing PRb6 octahedra. The corner-sharing octahedral tilt angles are 0°.