Mn3Si2Te6 is Spinel-like structured and crystallizes in the trigonal P-31c space group. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to six equivalent Te(1) atoms to form MnTe6 octahedra that share corners with three equivalent Mn(2)Te6 octahedra, corners with six equivalent Si(1)SiTe3 tetrahedra, edges with three equivalent Mn(1)Te6 octahedra, and  a faceface with one Mn(2)Te6 octahedra. The corner-sharing octahedral tilt angles are 44°. In the second Mn site, Mn(2) is bonded to six equivalent Te(1) atoms to form MnTe6 octahedra that share corners with six equivalent Mn(1)Te6 octahedra, corners with six equivalent Si(1)SiTe3 tetrahedra, and faces with two equivalent Mn(1)Te6 octahedra. The corner-sharing octahedral tilt angles are 44°. Si(1) is bonded to one Si(1) and three equivalent Te(1) atoms to form SiSiTe3 tetrahedra that share corners with three equivalent Mn(2)Te6 octahedra and corners with six equivalent Mn(1)Te6 octahedra. The corner-sharing octahedral tilt angles range from 58-77°. Te(1) is bonded in a distorted rectangular see-saw-like geometry to one Mn(2), two equivalent Mn(1), and one Si(1) atom.
Mn3Si2Te6 is Spinel-like structured and crystallizes in the trigonal P-31c space group. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to six equivalent Te(1) atoms to form MnTe6 octahedra that share corners with three equivalent Mn(2)Te6 octahedra, corners with six equivalent Si(1)SiTe3 tetrahedra, edges with three equivalent Mn(1)Te6 octahedra, and  a faceface with one Mn(2)Te6 octahedra. The corner-sharing octahedral tilt angles are 44°. There are three shorter (2.89 Å) and three longer (2.91 Å) Mn(1)-Te(1) bond lengths. In the second Mn site, Mn(2) is bonded to six equivalent Te(1) atoms to form MnTe6 octahedra that share corners with six equivalent Mn(1)Te6 octahedra, corners with six equivalent Si(1)SiTe3 tetrahedra, and faces with two equivalent Mn(1)Te6 octahedra. The corner-sharing octahedral tilt angles are 44°. All Mn(2)-Te(1) bond lengths are 2.90 Å. Si(1) is bonded to one Si(1) and three equivalent Te(1) atoms to form SiSiTe3 tetrahedra that share corners with three equivalent Mn(2)Te6 octahedra and corners with six equivalent Mn(1)Te6 octahedra. The corner-sharing octahedral tilt angles range from 58-77°. The Si(1)-Si(1) bond length is 2.39 Å. All Si(1)-Te(1) bond lengths are 2.55 Å. Te(1) is bonded in a distorted rectangular see-saw-like geometry to one Mn(2), two equivalent Mn(1), and one Si(1) atom.