Na5AgGe2S7 crystallizes in the monoclinic C2/c space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded to one S(3), one S(4), two equivalent S(1), and two equivalent S(2) atoms to form distorted NaS6 octahedra that share  a cornercorner with one Na(1)S6 octahedra,  a cornercorner with one Na(2)S6 octahedra,  a cornercorner with one Ge(1)S4 tetrahedra, edges with two equivalent Na(1)S6 octahedra, edges with two equivalent Na(2)S6 octahedra, and edges with three equivalent Ge(1)S4 tetrahedra. The corner-sharing octahedral tilt angles range from 8-39°. In the second Na site, Na(2) is bonded to two equivalent S(1), two equivalent S(2), and two equivalent S(3) atoms to form NaS6 octahedra that share corners with two equivalent Na(1)S6 octahedra, corners with two equivalent Ge(1)S4 tetrahedra, edges with four equivalent Na(1)S6 octahedra, and edges with two equivalent Ge(1)S4 tetrahedra. The corner-sharing octahedral tilt angles are 8°. In the third Na site, Na(3) is bonded in a distorted rectangular see-saw-like geometry to one S(2), one S(3), and two equivalent S(1) atoms. Ag(1) is bonded in a 4-coordinate geometry to two equivalent S(2) and two equivalent S(3) atoms. Ge(1) is bonded to one S(1), one S(2), one S(3), and one S(4) atom to form GeS4 tetrahedra that share  a cornercorner with one Na(1)S6 octahedra,  a cornercorner with one Na(2)S6 octahedra,  a cornercorner with one Ge(1)S4 tetrahedra,  an edgeedge with one Na(2)S6 octahedra, and edges with three equivalent Na(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 19-62°. There are four inequivalent S sites. In the first S site, S(1) is bonded to one Na(2), two equivalent Na(1), two equivalent Na(3), and one Ge(1) atom to form SNa5Ge octahedra that share  a cornercorner with one S(2)Na4AgGe octahedra,  a cornercorner with one S(1)Na5Ge octahedra, corners with five equivalent S(3)Na3AgGe trigonal bipyramids, edges with two equivalent S(1)Na5Ge octahedra, edges with four equivalent S(2)Na4AgGe octahedra, and  an edgeedge with one S(3)Na3AgGe trigonal bipyramid. The corner-sharing octahedral tilt angles range from 0-8°. In the second S site, S(2) is bonded to one Na(2), one Na(3), two equivalent Na(1), one Ag(1), and one Ge(1) atom to form SNa4AgGe octahedra that share  a cornercorner with one S(1)Na5Ge octahedra, corners with two equivalent S(2)Na4AgGe octahedra, corners with two equivalent S(3)Na3AgGe trigonal bipyramids,  an edgeedge with one S(2)Na4AgGe octahedra, edges with four equivalent S(1)Na5Ge octahedra, and edges with three equivalent S(3)Na3AgGe trigonal bipyramids. The corner-sharing octahedral tilt angles range from 0-75°. In the third S site, S(3) is bonded to one Na(1), one Na(2), one Na(3), one Ag(1), and one Ge(1) atom to form distorted SNa3AgGe trigonal bipyramids that share corners with two equivalent S(2)Na4AgGe octahedra, corners with five equivalent S(1)Na5Ge octahedra, corners with two equivalent S(3)Na3AgGe trigonal bipyramids,  an edgeedge with one S(1)Na5Ge octahedra, and edges with three equivalent S(2)Na4AgGe octahedra. The corner-sharing octahedral tilt angles range from 18-78°. In the fourth S site, S(4) is bonded in a 4-coordinate geometry to two equivalent Na(1) and two equivalent Ge(1) atoms.
Na5AgGe2S7 crystallizes in the monoclinic C2/c space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded to one S(3), one S(4), two equivalent S(1), and two equivalent S(2) atoms to form distorted NaS6 octahedra that share  a cornercorner with one Na(1)S6 octahedra,  a cornercorner with one Na(2)S6 octahedra,  a cornercorner with one Ge(1)S4 tetrahedra, edges with two equivalent Na(1)S6 octahedra, edges with two equivalent Na(2)S6 octahedra, and edges with three equivalent Ge(1)S4 tetrahedra. The corner-sharing octahedral tilt angles range from 8-39°. The Na(1)-S(3) bond length is 2.94 Å. The Na(1)-S(4) bond length is 3.17 Å. There is one shorter (2.89 Å) and one longer (2.94 Å) Na(1)-S(1) bond length. There is one shorter (3.01 Å) and one longer (3.04 Å) Na(1)-S(2) bond length. In the second Na site, Na(2) is bonded to two equivalent S(1), two equivalent S(2), and two equivalent S(3) atoms to form NaS6 octahedra that share corners with two equivalent Na(1)S6 octahedra, corners with two equivalent Ge(1)S4 tetrahedra, edges with four equivalent Na(1)S6 octahedra, and edges with two equivalent Ge(1)S4 tetrahedra. The corner-sharing octahedral tilt angles are 8°. Both Na(2)-S(1) bond lengths are 2.83 Å. Both Na(2)-S(2) bond lengths are 3.07 Å. Both Na(2)-S(3) bond lengths are 2.98 Å. In the third Na site, Na(3) is bonded in a distorted rectangular see-saw-like geometry to one S(2), one S(3), and two equivalent S(1) atoms. The Na(3)-S(2) bond length is 2.91 Å. The Na(3)-S(3) bond length is 2.81 Å. There is one shorter (2.85 Å) and one longer (2.93 Å) Na(3)-S(1) bond length. Ag(1) is bonded in a 4-coordinate geometry to two equivalent S(2) and two equivalent S(3) atoms. Both Ag(1)-S(2) bond lengths are 2.60 Å. Both Ag(1)-S(3) bond lengths are 2.69 Å. Ge(1) is bonded to one S(1), one S(2), one S(3), and one S(4) atom to form GeS4 tetrahedra that share  a cornercorner with one Na(1)S6 octahedra,  a cornercorner with one Na(2)S6 octahedra,  a cornercorner with one Ge(1)S4 tetrahedra,  an edgeedge with one Na(2)S6 octahedra, and edges with three equivalent Na(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 19-62°. The Ge(1)-S(1) bond length is 2.22 Å. The Ge(1)-S(2) bond length is 2.21 Å. The Ge(1)-S(3) bond length is 2.22 Å. The Ge(1)-S(4) bond length is 2.28 Å. There are four inequivalent S sites. In the first S site, S(1) is bonded to one Na(2), two equivalent Na(1), two equivalent Na(3), and one Ge(1) atom to form SNa5Ge octahedra that share  a cornercorner with one S(2)Na4AgGe octahedra,  a cornercorner with one S(1)Na5Ge octahedra, corners with five equivalent S(3)Na3AgGe trigonal bipyramids, edges with two equivalent S(1)Na5Ge octahedra, edges with four equivalent S(2)Na4AgGe octahedra, and  an edgeedge with one S(3)Na3AgGe trigonal bipyramid. The corner-sharing octahedral tilt angles range from 0-8°. In the second S site, S(2) is bonded to one Na(2), one Na(3), two equivalent Na(1), one Ag(1), and one Ge(1) atom to form SNa4AgGe octahedra that share  a cornercorner with one S(1)Na5Ge octahedra, corners with two equivalent S(2)Na4AgGe octahedra, corners with two equivalent S(3)Na3AgGe trigonal bipyramids,  an edgeedge with one S(2)Na4AgGe octahedra, edges with four equivalent S(1)Na5Ge octahedra, and edges with three equivalent S(3)Na3AgGe trigonal bipyramids. The corner-sharing octahedral tilt angles range from 0-75°. In the third S site, S(3) is bonded to one Na(1), one Na(2), one Na(3), one Ag(1), and one Ge(1) atom to form distorted SNa3AgGe trigonal bipyramids that share corners with two equivalent S(2)Na4AgGe octahedra, corners with five equivalent S(1)Na5Ge octahedra, corners with two equivalent S(3)Na3AgGe trigonal bipyramids,  an edgeedge with one S(1)Na5Ge octahedra, and edges with three equivalent S(2)Na4AgGe octahedra. The corner-sharing octahedral tilt angles range from 18-78°. In the fourth S site, S(4) is bonded in a 4-coordinate geometry to two equivalent Na(1) and two equivalent Ge(1) atoms.