Na4PbGe2S6 crystallizes in the monoclinic C2 space group. There are four inequivalent Na sites. In the first Na site, Na(1) 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(4)S6 octahedra, corners with two equivalent Pb(1)S6 octahedra, edges with two equivalent Na(4)S6 octahedra, edges with two equivalent Pb(1)S6 octahedra, edges with three equivalent Na(2)S6 octahedra, and edges with three equivalent Na(3)S6 octahedra. The corner-sharing octahedral tilt angles range from 7-8°. 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(4)S6 octahedra, corners with two equivalent Pb(1)S6 octahedra, edges with two equivalent Na(4)S6 octahedra, edges with two equivalent Pb(1)S6 octahedra, edges with three equivalent Na(1)S6 octahedra, and edges with three equivalent Na(3)S6 octahedra. The corner-sharing octahedral tilt angles range from 7-8°. In the third Na site, Na(3) 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(4)S6 octahedra, corners with two equivalent Pb(1)S6 octahedra, edges with two equivalent Na(4)S6 octahedra, edges with two equivalent Pb(1)S6 octahedra, edges with three equivalent Na(1)S6 octahedra, and edges with three equivalent Na(2)S6 octahedra. The corner-sharing octahedral tilt angles are 6°. In the fourth Na site, Na(4) 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 Na(2)S6 octahedra, corners with two equivalent Na(3)S6 octahedra, edges with two equivalent Na(1)S6 octahedra, edges with two equivalent Na(2)S6 octahedra, edges with two equivalent Na(3)S6 octahedra, and edges with three equivalent Pb(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 6-8°. Pb(1) is bonded to two equivalent S(1), two equivalent S(2), and two equivalent S(3) atoms to form PbS6 octahedra that share corners with two equivalent Na(1)S6 octahedra, corners with two equivalent Na(2)S6 octahedra, corners with two equivalent Na(3)S6 octahedra, edges with two equivalent Na(1)S6 octahedra, edges with two equivalent Na(2)S6 octahedra, edges with two equivalent Na(3)S6 octahedra, and edges with three equivalent Na(4)S6 octahedra. The corner-sharing octahedral tilt angles range from 6-8°. Ge(1) is bonded in a distorted trigonal non-coplanar geometry to one S(1), one S(2), and one S(3) atom. There are three inequivalent S sites. In the first S site, S(1) is bonded to one Na(1), one Na(2), one Na(3), one Na(4), one Pb(1), and one Ge(1) atom to form a mixture of distorted corner and edge-sharing SNa4GePb octahedra. The corner-sharing octahedral tilt angles range from 0-89°. In the second S site, S(2) is bonded to one Na(1), one Na(2), one Na(3), one Na(4), one Pb(1), and one Ge(1) atom to form a mixture of distorted corner and edge-sharing SNa4GePb octahedra. The corner-sharing octahedral tilt angles range from 0-89°. In the third S site, S(3) is bonded to one Na(1), one Na(2), one Na(3), one Na(4), one Pb(1), and one Ge(1) atom to form a mixture of distorted corner and edge-sharing SNa4GePb octahedra. The corner-sharing octahedral tilt angles range from 0-89°.
Na4PbGe2S6 crystallizes in the monoclinic C2 space group. There are four inequivalent Na sites. In the first Na site, Na(1) 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(4)S6 octahedra, corners with two equivalent Pb(1)S6 octahedra, edges with two equivalent Na(4)S6 octahedra, edges with two equivalent Pb(1)S6 octahedra, edges with three equivalent Na(2)S6 octahedra, and edges with three equivalent Na(3)S6 octahedra. The corner-sharing octahedral tilt angles range from 7-8°. Both Na(1)-S(1) bond lengths are 2.91 Å. Both Na(1)-S(2) bond lengths are 2.99 Å. Both Na(1)-S(3) bond lengths are 2.99 Å. 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(4)S6 octahedra, corners with two equivalent Pb(1)S6 octahedra, edges with two equivalent Na(4)S6 octahedra, edges with two equivalent Pb(1)S6 octahedra, edges with three equivalent Na(1)S6 octahedra, and edges with three equivalent Na(3)S6 octahedra. The corner-sharing octahedral tilt angles range from 7-8°. Both Na(2)-S(1) bond lengths are 2.99 Å. Both Na(2)-S(2) bond lengths are 2.91 Å. Both Na(2)-S(3) bond lengths are 3.00 Å. In the third Na site, Na(3) 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(4)S6 octahedra, corners with two equivalent Pb(1)S6 octahedra, edges with two equivalent Na(4)S6 octahedra, edges with two equivalent Pb(1)S6 octahedra, edges with three equivalent Na(1)S6 octahedra, and edges with three equivalent Na(2)S6 octahedra. The corner-sharing octahedral tilt angles are 6°. Both Na(3)-S(1) bond lengths are 2.91 Å. Both Na(3)-S(2) bond lengths are 2.91 Å. Both Na(3)-S(3) bond lengths are 3.08 Å. In the fourth Na site, Na(4) 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 Na(2)S6 octahedra, corners with two equivalent Na(3)S6 octahedra, edges with two equivalent Na(1)S6 octahedra, edges with two equivalent Na(2)S6 octahedra, edges with two equivalent Na(3)S6 octahedra, and edges with three equivalent Pb(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 6-8°. Both Na(4)-S(1) bond lengths are 3.05 Å. Both Na(4)-S(2) bond lengths are 3.05 Å. Both Na(4)-S(3) bond lengths are 3.04 Å. Pb(1) is bonded to two equivalent S(1), two equivalent S(2), and two equivalent S(3) atoms to form PbS6 octahedra that share corners with two equivalent Na(1)S6 octahedra, corners with two equivalent Na(2)S6 octahedra, corners with two equivalent Na(3)S6 octahedra, edges with two equivalent Na(1)S6 octahedra, edges with two equivalent Na(2)S6 octahedra, edges with two equivalent Na(3)S6 octahedra, and edges with three equivalent Na(4)S6 octahedra. The corner-sharing octahedral tilt angles range from 6-8°. Both Pb(1)-S(1) bond lengths are 3.04 Å. Both Pb(1)-S(2) bond lengths are 3.05 Å. Both Pb(1)-S(3) bond lengths are 3.03 Å. Ge(1) is bonded in a distorted trigonal non-coplanar geometry to one S(1), one S(2), and one S(3) atom. The Ge(1)-S(1) bond length is 2.25 Å. The Ge(1)-S(2) bond length is 2.25 Å. The Ge(1)-S(3) bond length is 2.24 Å. There are three inequivalent S sites. In the first S site, S(1) is bonded to one Na(1), one Na(2), one Na(3), one Na(4), one Pb(1), and one Ge(1) atom to form a mixture of distorted corner and edge-sharing SNa4GePb octahedra. The corner-sharing octahedral tilt angles range from 0-89°. In the second S site, S(2) is bonded to one Na(1), one Na(2), one Na(3), one Na(4), one Pb(1), and one Ge(1) atom to form a mixture of distorted corner and edge-sharing SNa4GePb octahedra. The corner-sharing octahedral tilt angles range from 0-89°. In the third S site, S(3) is bonded to one Na(1), one Na(2), one Na(3), one Na(4), one Pb(1), and one Ge(1) atom to form a mixture of distorted corner and edge-sharing SNa4GePb octahedra. The corner-sharing octahedral tilt angles range from 0-89°.