Fe2GeS4 is Spinel-like structured and crystallizes in the orthorhombic Pnma space group. There are two inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to two equivalent S(1), two equivalent S(2), and two equivalent S(3) atoms to form FeS6 octahedra that share corners with four equivalent Fe(2)S6 octahedra, corners with two equivalent Ge(1)S4 tetrahedra, edges with two equivalent Fe(1)S6 octahedra, edges with two equivalent Fe(2)S6 octahedra, and edges with two equivalent Ge(1)S4 tetrahedra. The corner-sharing octahedral tilt angles range from 49-50°. In the second Fe site, Fe(2) is bonded to one S(1), one S(2), and four equivalent S(3) atoms to form FeS6 octahedra that share corners with four equivalent Fe(1)S6 octahedra, corners with four equivalent Fe(2)S6 octahedra, corners with four equivalent Ge(1)S4 tetrahedra, edges with two equivalent Fe(1)S6 octahedra, and  an edgeedge with one Ge(1)S4 tetrahedra. The corner-sharing octahedral tilt angles range from 47-50°. Ge(1) is bonded to one S(1), one S(2), and two equivalent S(3) atoms to form distorted GeS4 tetrahedra that share corners with two equivalent Fe(1)S6 octahedra, corners with four equivalent Fe(2)S6 octahedra,  an edgeedge with one Fe(2)S6 octahedra, and edges with two equivalent Fe(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 67-69°. There are three inequivalent S sites. In the first S site, S(1) is bonded in a rectangular see-saw-like geometry to one Fe(2), two equivalent Fe(1), and one Ge(1) atom. In the second S site, S(2) is bonded to one Fe(2), two equivalent Fe(1), and one Ge(1) atom to form corner-sharing SFe3Ge tetrahedra. In the third S site, S(3) is bonded in a rectangular see-saw-like geometry to one Fe(1), two equivalent Fe(2), and one Ge(1) atom.
Fe2GeS4 is Spinel-like structured and crystallizes in the orthorhombic Pnma space group. There are two inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to two equivalent S(1), two equivalent S(2), and two equivalent S(3) atoms to form FeS6 octahedra that share corners with four equivalent Fe(2)S6 octahedra, corners with two equivalent Ge(1)S4 tetrahedra, edges with two equivalent Fe(1)S6 octahedra, edges with two equivalent Fe(2)S6 octahedra, and edges with two equivalent Ge(1)S4 tetrahedra. The corner-sharing octahedral tilt angles range from 49-50°. Both Fe(1)-S(1) bond lengths are 2.36 Å. Both Fe(1)-S(2) bond lengths are 2.20 Å. Both Fe(1)-S(3) bond lengths are 2.38 Å. In the second Fe site, Fe(2) is bonded to one S(1), one S(2), and four equivalent S(3) atoms to form FeS6 octahedra that share corners with four equivalent Fe(1)S6 octahedra, corners with four equivalent Fe(2)S6 octahedra, corners with four equivalent Ge(1)S4 tetrahedra, edges with two equivalent Fe(1)S6 octahedra, and  an edgeedge with one Ge(1)S4 tetrahedra. The corner-sharing octahedral tilt angles range from 47-50°. The Fe(2)-S(1) bond length is 2.30 Å. The Fe(2)-S(2) bond length is 2.22 Å. There are two shorter (2.31 Å) and two longer (2.51 Å) Fe(2)-S(3) bond lengths. Ge(1) is bonded to one S(1), one S(2), and two equivalent S(3) atoms to form distorted GeS4 tetrahedra that share corners with two equivalent Fe(1)S6 octahedra, corners with four equivalent Fe(2)S6 octahedra,  an edgeedge with one Fe(2)S6 octahedra, and edges with two equivalent Fe(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 67-69°. The Ge(1)-S(1) bond length is 2.26 Å. The Ge(1)-S(2) bond length is 2.27 Å. Both Ge(1)-S(3) bond lengths are 2.26 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 Fe(2), two equivalent Fe(1), and one Ge(1) atom. In the second S site, S(2) is bonded to one Fe(2), two equivalent Fe(1), and one Ge(1) atom to form corner-sharing SFe3Ge tetrahedra. In the third S site, S(3) is bonded in a rectangular see-saw-like geometry to one Fe(1), two equivalent Fe(2), and one Ge(1) atom.