MgCe2S4 is Spinel-like structured and crystallizes in the orthorhombic Pnma space group. Mg(1) is bonded to one S(2), one S(3), and two equivalent S(1) atoms to form MgS4 tetrahedra that share corners with two equivalent Ce(1)S6 octahedra, corners with four equivalent Ce(2)S6 octahedra,  an edgeedge with one Ce(2)S6 octahedra, and edges with two equivalent Ce(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 60-62°. There are two inequivalent Ce sites. In the first Ce site, Ce(1) is bonded to two equivalent S(1), two equivalent S(2), and two equivalent S(3) atoms to form CeS6 octahedra that share corners with four equivalent Ce(2)S6 octahedra, corners with two equivalent Mg(1)S4 tetrahedra, edges with two equivalent Ce(1)S6 octahedra, edges with two equivalent Ce(2)S6 octahedra, and edges with two equivalent Mg(1)S4 tetrahedra. The corner-sharing octahedral tilt angles range from 53-58°. In the second Ce site, Ce(2) is bonded to one S(2), one S(3), and four equivalent S(1) atoms to form CeS6 octahedra that share corners with four equivalent Ce(1)S6 octahedra, corners with four equivalent Ce(2)S6 octahedra, corners with four equivalent Mg(1)S4 tetrahedra, edges with two equivalent Ce(1)S6 octahedra, and  an edgeedge with one Mg(1)S4 tetrahedra. The corner-sharing octahedral tilt angles range from 48-58°. There are three inequivalent S sites. In the first S site, S(1) is bonded in a rectangular see-saw-like geometry to one Mg(1), one Ce(1), and two equivalent Ce(2) atoms. In the second S site, S(2) is bonded in a rectangular see-saw-like geometry to one Mg(1), one Ce(2), and two equivalent Ce(1) atoms. In the third S site, S(3) is bonded to one Mg(1), one Ce(2), and two equivalent Ce(1) atoms to form distorted corner-sharing SCe3Mg tetrahedra.
MgCe2S4 is Spinel-like structured and crystallizes in the orthorhombic Pnma space group. Mg(1) is bonded to one S(2), one S(3), and two equivalent S(1) atoms to form MgS4 tetrahedra that share corners with two equivalent Ce(1)S6 octahedra, corners with four equivalent Ce(2)S6 octahedra,  an edgeedge with one Ce(2)S6 octahedra, and edges with two equivalent Ce(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 60-62°. The Mg(1)-S(2) bond length is 2.48 Å. The Mg(1)-S(3) bond length is 2.42 Å. Both Mg(1)-S(1) bond lengths are 2.48 Å. There are two inequivalent Ce sites. In the first Ce site, Ce(1) is bonded to two equivalent S(1), two equivalent S(2), and two equivalent S(3) atoms to form CeS6 octahedra that share corners with four equivalent Ce(2)S6 octahedra, corners with two equivalent Mg(1)S4 tetrahedra, edges with two equivalent Ce(1)S6 octahedra, edges with two equivalent Ce(2)S6 octahedra, and edges with two equivalent Mg(1)S4 tetrahedra. The corner-sharing octahedral tilt angles range from 53-58°. Both Ce(1)-S(1) bond lengths are 2.88 Å. Both Ce(1)-S(2) bond lengths are 2.85 Å. Both Ce(1)-S(3) bond lengths are 2.84 Å. In the second Ce site, Ce(2) is bonded to one S(2), one S(3), and four equivalent S(1) atoms to form CeS6 octahedra that share corners with four equivalent Ce(1)S6 octahedra, corners with four equivalent Ce(2)S6 octahedra, corners with four equivalent Mg(1)S4 tetrahedra, edges with two equivalent Ce(1)S6 octahedra, and  an edgeedge with one Mg(1)S4 tetrahedra. The corner-sharing octahedral tilt angles range from 48-58°. The Ce(2)-S(2) bond length is 2.84 Å. The Ce(2)-S(3) bond length is 2.86 Å. All Ce(2)-S(1) bond lengths are 2.93 Å. There are three inequivalent S sites. In the first S site, S(1) is bonded in a rectangular see-saw-like geometry to one Mg(1), one Ce(1), and two equivalent Ce(2) atoms. In the second S site, S(2) is bonded in a rectangular see-saw-like geometry to one Mg(1), one Ce(2), and two equivalent Ce(1) atoms. In the third S site, S(3) is bonded to one Mg(1), one Ce(2), and two equivalent Ce(1) atoms to form distorted corner-sharing SCe3Mg tetrahedra.