Ca(CeTe2)2 crystallizes in the tetragonal I-42d space group. Ca(1) is bonded to eight equivalent Te(1) atoms to form distorted CaTe8 hexagonal bipyramids that share corners with eight equivalent Ce(1)Te8 hexagonal bipyramids, edges with four equivalent Ca(1)Te8 hexagonal bipyramids, and faces with eight equivalent Ce(1)Te8 hexagonal bipyramids. Ce(1) is bonded to eight equivalent Te(1) atoms to form distorted CeTe8 hexagonal bipyramids that share corners with four equivalent Ca(1)Te8 hexagonal bipyramids, corners with four equivalent Ce(1)Te8 hexagonal bipyramids, edges with four equivalent Ce(1)Te8 hexagonal bipyramids, faces with four equivalent Ca(1)Te8 hexagonal bipyramids, and faces with four equivalent Ce(1)Te8 hexagonal bipyramids. Te(1) is bonded to two equivalent Ca(1) and four equivalent Ce(1) atoms to form a mixture of distorted corner, face, and edge-sharing TeCa2Ce4 octahedra. The corner-sharing octahedral tilt angles range from 17-50°.
Ca(CeTe2)2 crystallizes in the tetragonal I-42d space group. Ca(1) is bonded to eight equivalent Te(1) atoms to form distorted CaTe8 hexagonal bipyramids that share corners with eight equivalent Ce(1)Te8 hexagonal bipyramids, edges with four equivalent Ca(1)Te8 hexagonal bipyramids, and faces with eight equivalent Ce(1)Te8 hexagonal bipyramids. There are four shorter (3.20 Å) and four longer (3.45 Å) Ca(1)-Te(1) bond lengths. Ce(1) is bonded to eight equivalent Te(1) atoms to form distorted CeTe8 hexagonal bipyramids that share corners with four equivalent Ca(1)Te8 hexagonal bipyramids, corners with four equivalent Ce(1)Te8 hexagonal bipyramids, edges with four equivalent Ce(1)Te8 hexagonal bipyramids, faces with four equivalent Ca(1)Te8 hexagonal bipyramids, and faces with four equivalent Ce(1)Te8 hexagonal bipyramids. There are a spread of Ce(1)-Te(1) bond distances ranging from 3.22-3.42 Å. Te(1) is bonded to two equivalent Ca(1) and four equivalent Ce(1) atoms to form a mixture of distorted corner, face, and edge-sharing TeCa2Ce4 octahedra. The corner-sharing octahedral tilt angles range from 17-50°.