Nb3GeS6 is Ilmenite-like structured and crystallizes in the hexagonal P6_3/mcm space group. There are two inequivalent Nb sites. In the first Nb site, Nb(1) is bonded to six equivalent S(1) atoms to form distorted NbS6 pentagonal pyramids that share corners with six equivalent Ge(1)S6 octahedra, edges with three equivalent Nb(1)S6 pentagonal pyramids, and edges with three equivalent Nb(2)S6 pentagonal pyramids. The corner-sharing octahedral tilt angles are 45°. In the second Nb site, Nb(2) is bonded to six equivalent S(1) atoms to form distorted NbS6 pentagonal pyramids that share edges with six equivalent Nb(1)S6 pentagonal pyramids and faces with two equivalent Ge(1)S6 octahedra. Ge(1) is bonded to six equivalent S(1) atoms to form distorted GeS6 octahedra that share corners with twelve equivalent Nb(1)S6 pentagonal pyramids and faces with two equivalent Nb(2)S6 pentagonal pyramids. S(1) is bonded to one Nb(2), two equivalent Nb(1), and one Ge(1) atom to form a mixture of edge, face, and corner-sharing SNb3Ge trigonal pyramids.
Nb3GeS6 is Ilmenite-like structured and crystallizes in the hexagonal P6_3/mcm space group. There are two inequivalent Nb sites. In the first Nb site, Nb(1) is bonded to six equivalent S(1) atoms to form distorted NbS6 pentagonal pyramids that share corners with six equivalent Ge(1)S6 octahedra, edges with three equivalent Nb(1)S6 pentagonal pyramids, and edges with three equivalent Nb(2)S6 pentagonal pyramids. The corner-sharing octahedral tilt angles are 45°. All Nb(1)-S(1) bond lengths are 2.49 Å. In the second Nb site, Nb(2) is bonded to six equivalent S(1) atoms to form distorted NbS6 pentagonal pyramids that share edges with six equivalent Nb(1)S6 pentagonal pyramids and faces with two equivalent Ge(1)S6 octahedra. All Nb(2)-S(1) bond lengths are 2.50 Å. Ge(1) is bonded to six equivalent S(1) atoms to form distorted GeS6 octahedra that share corners with twelve equivalent Nb(1)S6 pentagonal pyramids and faces with two equivalent Nb(2)S6 pentagonal pyramids. All Ge(1)-S(1) bond lengths are 2.66 Å. S(1) is bonded to one Nb(2), two equivalent Nb(1), and one Ge(1) atom to form a mixture of edge, face, and corner-sharing SNb3Ge trigonal pyramids.