Mn2SiS4 is Spinel-like structured and crystallizes in the orthorhombic Pnma space group. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one S(2), one S(3), and four equivalent S(1) atoms to form MnS6 octahedra that share corners with four equivalent Mn(1)S6 octahedra, corners with four equivalent Mn(2)S6 octahedra, corners with four equivalent Si(1)S4 tetrahedra, edges with two equivalent Mn(2)S6 octahedra, and  an edgeedge with one Si(1)S4 tetrahedra. The corner-sharing octahedral tilt angles range from 49-59°. In the second Mn site, Mn(2) is bonded to two equivalent S(1), two equivalent S(2), and two equivalent S(3) atoms to form MnS6 octahedra that share corners with four equivalent Mn(1)S6 octahedra, corners with two equivalent Si(1)S4 tetrahedra, edges with two equivalent Mn(1)S6 octahedra, edges with two equivalent Mn(2)S6 octahedra, and edges with two equivalent Si(1)S4 tetrahedra. The corner-sharing octahedral tilt angles range from 52-59°. Si(1) is bonded to one S(2), one S(3), and two equivalent S(1) atoms to form SiS4 tetrahedra that share corners with two equivalent Mn(2)S6 octahedra, corners with four equivalent Mn(1)S6 octahedra,  an edgeedge with one Mn(1)S6 octahedra, and edges with two equivalent Mn(2)S6 octahedra. The corner-sharing octahedral tilt angles are 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 Mn(2), two equivalent Mn(1), and one Si(1) atom. In the second S site, S(2) is bonded to one Mn(1), two equivalent Mn(2), and one Si(1) atom to form distorted corner-sharing SMn3Si trigonal pyramids. In the third S site, S(3) is bonded in a rectangular see-saw-like geometry to one Mn(1), two equivalent Mn(2), and one Si(1) atom.
Mn2SiS4 is Spinel-like structured and crystallizes in the orthorhombic Pnma space group. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one S(2), one S(3), and four equivalent S(1) atoms to form MnS6 octahedra that share corners with four equivalent Mn(1)S6 octahedra, corners with four equivalent Mn(2)S6 octahedra, corners with four equivalent Si(1)S4 tetrahedra, edges with two equivalent Mn(2)S6 octahedra, and  an edgeedge with one Si(1)S4 tetrahedra. The corner-sharing octahedral tilt angles range from 49-59°. The Mn(1)-S(2) bond length is 2.62 Å. The Mn(1)-S(3) bond length is 2.56 Å. There are two shorter (2.61 Å) and two longer (2.63 Å) Mn(1)-S(1) bond lengths. In the second Mn site, Mn(2) is bonded to two equivalent S(1), two equivalent S(2), and two equivalent S(3) atoms to form MnS6 octahedra that share corners with four equivalent Mn(1)S6 octahedra, corners with two equivalent Si(1)S4 tetrahedra, edges with two equivalent Mn(1)S6 octahedra, edges with two equivalent Mn(2)S6 octahedra, and edges with two equivalent Si(1)S4 tetrahedra. The corner-sharing octahedral tilt angles range from 52-59°. Both Mn(2)-S(1) bond lengths are 2.61 Å. Both Mn(2)-S(2) bond lengths are 2.61 Å. Both Mn(2)-S(3) bond lengths are 2.56 Å. Si(1) is bonded to one S(2), one S(3), and two equivalent S(1) atoms to form SiS4 tetrahedra that share corners with two equivalent Mn(2)S6 octahedra, corners with four equivalent Mn(1)S6 octahedra,  an edgeedge with one Mn(1)S6 octahedra, and edges with two equivalent Mn(2)S6 octahedra. The corner-sharing octahedral tilt angles are 58°. The Si(1)-S(2) bond length is 2.10 Å. The Si(1)-S(3) bond length is 2.14 Å. Both Si(1)-S(1) bond lengths are 2.14 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 Mn(2), two equivalent Mn(1), and one Si(1) atom. In the second S site, S(2) is bonded to one Mn(1), two equivalent Mn(2), and one Si(1) atom to form distorted corner-sharing SMn3Si trigonal pyramids. In the third S site, S(3) is bonded in a rectangular see-saw-like geometry to one Mn(1), two equivalent Mn(2), and one Si(1) atom.