Ba4Ge2PbS8Br2 crystallizes in the orthorhombic Pmn2_1 space group. There are two inequivalent Ba sites. In the first Ba site, Ba(1) is bonded in a 8-coordinate geometry to one S(1), one S(2), one S(3), one S(4), two equivalent S(5), and two equivalent Br(1) atoms. In the second Ba site, Ba(2) is bonded in a 8-coordinate geometry to one S(1), one S(2), one S(3), one S(4), two equivalent S(6), and two equivalent Br(2) atoms. Pb(1) is bonded to one S(6), two equivalent S(1), two equivalent S(2), and one Br(1) atom to form distorted PbS5Br octahedra that share corners with three equivalent Ge(2)S4 tetrahedra and  an edgeedge with one Ge(1)S4 tetrahedra. There are two inequivalent Ge sites. In the first Ge site, Ge(1) is bonded to one S(4), one S(5), and two equivalent S(1) atoms to form GeS4 tetrahedra that share  an edgeedge with one Pb(1)S5Br octahedra. In the second Ge site, Ge(2) is bonded to one S(3), one S(6), and two equivalent S(2) atoms to form GeS4 tetrahedra that share corners with three equivalent Pb(1)S5Br octahedra. The corner-sharing octahedral tilt angles range from 5-16°. There are six inequivalent S sites. In the first S site, S(1) is bonded to one Ba(1), one Ba(2), one Pb(1), and one Ge(1) atom to form distorted SBa2GePb trigonal pyramids that share  a cornercorner with one S(6)Ba4GePb octahedra,  a cornercorner with one S(4)Ba4Ge square pyramid,  a cornercorner with one S(5)Ba4Ge square pyramid,  a cornercorner with one Br(1)Ba4Pb square pyramid, corners with two equivalent S(3)Ba4Ge square pyramids,  an edgeedge with one S(6)Ba4GePb octahedra,  an edgeedge with one S(4)Ba4Ge square pyramid,  an edgeedge with one S(5)Ba4Ge square pyramid,  an edgeedge with one Br(1)Ba4Pb square pyramid, and  an edgeedge with one S(1)Ba2GePb trigonal pyramid. The corner-sharing octahedral tilt angles are 43°. In the second S site, S(2) is bonded in a 1-coordinate geometry to one Ba(1), one Ba(2), one Pb(1), and one Ge(2) atom. In the third S site, S(3) is bonded to two equivalent Ba(1), two equivalent Ba(2), and one Ge(2) atom to form distorted SBa4Ge square pyramids that share corners with two equivalent S(6)Ba4GePb octahedra, corners with two equivalent S(5)Ba4Ge square pyramids, corners with two equivalent Br(1)Ba4Pb square pyramids, corners with four equivalent S(1)Ba2GePb trigonal pyramids,  an edgeedge with one S(5)Ba4Ge square pyramid,  an edgeedge with one Br(1)Ba4Pb square pyramid, edges with two equivalent S(4)Ba4Ge square pyramids, and  a faceface with one S(6)Ba4GePb octahedra. The corner-sharing octahedral tilt angles are 39°. In the fourth S site, S(4) is bonded to two equivalent Ba(1), two equivalent Ba(2), and one Ge(1) atom to form distorted SBa4Ge square pyramids that share corners with two equivalent S(6)Ba4GePb octahedra, corners with two equivalent S(5)Ba4Ge square pyramids, corners with two equivalent Br(1)Ba4Pb square pyramids, corners with two equivalent S(1)Ba2GePb trigonal pyramids,  an edgeedge with one S(6)Ba4GePb octahedra,  an edgeedge with one Br(1)Ba4Pb square pyramid, edges with two equivalent S(3)Ba4Ge square pyramids, edges with two equivalent S(1)Ba2GePb trigonal pyramids, and  a faceface with one S(5)Ba4Ge square pyramid. The corner-sharing octahedral tilt angles are 58°. In the fifth S site, S(5) is bonded to four equivalent Ba(1) and one Ge(1) atom to form distorted SBa4Ge square pyramids that share corners with two equivalent S(3)Ba4Ge square pyramids, corners with two equivalent S(4)Ba4Ge square pyramids, corners with four equivalent S(5)Ba4Ge square pyramids, corners with two equivalent S(1)Ba2GePb trigonal pyramids,  an edgeedge with one S(3)Ba4Ge square pyramid, edges with four equivalent Br(1)Ba4Pb square pyramids, edges with two equivalent S(1)Ba2GePb trigonal pyramids, and  a faceface with one S(4)Ba4Ge square pyramid. In the sixth S site, S(6) is bonded to four equivalent Ba(2), one Pb(1), and one Ge(2) atom to form distorted SBa4GePb octahedra that share corners with four equivalent S(6)Ba4GePb octahedra,  a cornercorner with one Br(1)Ba4Pb square pyramid, corners with two equivalent S(3)Ba4Ge square pyramids, corners with two equivalent S(4)Ba4Ge square pyramids, corners with two equivalent S(1)Ba2GePb trigonal pyramids,  an edgeedge with one S(4)Ba4Ge square pyramid, edges with two equivalent S(1)Ba2GePb trigonal pyramids, and  a faceface with one S(3)Ba4Ge square pyramid. The corner-sharing octahedral tilt angles are 32°. There are two inequivalent Br sites. In the first Br site, Br(1) is bonded to four equivalent Ba(1) and one Pb(1) atom to form BrBa4Pb square pyramids that share  a cornercorner with one S(6)Ba4GePb octahedra, corners with two equivalent S(3)Ba4Ge square pyramids, corners with two equivalent S(4)Ba4Ge square pyramids, corners with four equivalent Br(1)Ba4Pb square pyramids, corners with two equivalent S(1)Ba2GePb trigonal pyramids,  an edgeedge with one S(3)Ba4Ge square pyramid,  an edgeedge with one S(4)Ba4Ge square pyramid, edges with four equivalent S(5)Ba4Ge square pyramids, and edges with two equivalent S(1)Ba2GePb trigonal pyramids. The corner-sharing octahedral tilt angles are 12°. In the second Br site, Br(2) is bonded in a square co-planar geometry to four equivalent Ba(2) atoms.
Ba4Ge2PbS8Br2 crystallizes in the orthorhombic Pmn2_1 space group. There are two inequivalent Ba sites. In the first Ba site, Ba(1) is bonded in a 8-coordinate geometry to one S(1), one S(2), one S(3), one S(4), two equivalent S(5), and two equivalent Br(1) atoms. The Ba(1)-S(1) bond length is 3.38 Å. The Ba(1)-S(2) bond length is 3.33 Å. The Ba(1)-S(3) bond length is 3.24 Å. The Ba(1)-S(4) bond length is 3.28 Å. There is one shorter (3.31 Å) and one longer (3.52 Å) Ba(1)-S(5) bond length. There is one shorter (3.35 Å) and one longer (3.48 Å) Ba(1)-Br(1) bond length. In the second Ba site, Ba(2) is bonded in a 8-coordinate geometry to one S(1), one S(2), one S(3), one S(4), two equivalent S(6), and two equivalent Br(2) atoms. The Ba(2)-S(1) bond length is 3.50 Å. The Ba(2)-S(2) bond length is 3.33 Å. The Ba(2)-S(3) bond length is 3.31 Å. The Ba(2)-S(4) bond length is 3.28 Å. There is one shorter (3.37 Å) and one longer (3.44 Å) Ba(2)-S(6) bond length. There is one shorter (3.35 Å) and one longer (3.46 Å) Ba(2)-Br(2) bond length. Pb(1) is bonded to one S(6), two equivalent S(1), two equivalent S(2), and one Br(1) atom to form distorted PbS5Br octahedra that share corners with three equivalent Ge(2)S4 tetrahedra and  an edgeedge with one Ge(1)S4 tetrahedra. The Pb(1)-S(6) bond length is 2.94 Å. Both Pb(1)-S(1) bond lengths are 2.80 Å. Both Pb(1)-S(2) bond lengths are 3.14 Å. The Pb(1)-Br(1) bond length is 3.12 Å. There are two inequivalent Ge sites. In the first Ge site, Ge(1) is bonded to one S(4), one S(5), and two equivalent S(1) atoms to form GeS4 tetrahedra that share  an edgeedge with one Pb(1)S5Br octahedra. The Ge(1)-S(4) bond length is 2.23 Å. The Ge(1)-S(5) bond length is 2.22 Å. Both Ge(1)-S(1) bond lengths are 2.23 Å. In the second Ge site, Ge(2) is bonded to one S(3), one S(6), and two equivalent S(2) atoms to form GeS4 tetrahedra that share corners with three equivalent Pb(1)S5Br octahedra. The corner-sharing octahedral tilt angles range from 5-16°. The Ge(2)-S(3) bond length is 2.24 Å. The Ge(2)-S(6) bond length is 2.32 Å. Both Ge(2)-S(2) bond lengths are 2.20 Å. There are six inequivalent S sites. In the first S site, S(1) is bonded to one Ba(1), one Ba(2), one Pb(1), and one Ge(1) atom to form distorted SBa2GePb trigonal pyramids that share  a cornercorner with one S(6)Ba4GePb octahedra,  a cornercorner with one S(4)Ba4Ge square pyramid,  a cornercorner with one S(5)Ba4Ge square pyramid,  a cornercorner with one Br(1)Ba4Pb square pyramid, corners with two equivalent S(3)Ba4Ge square pyramids,  an edgeedge with one S(6)Ba4GePb octahedra,  an edgeedge with one S(4)Ba4Ge square pyramid,  an edgeedge with one S(5)Ba4Ge square pyramid,  an edgeedge with one Br(1)Ba4Pb square pyramid, and  an edgeedge with one S(1)Ba2GePb trigonal pyramid. The corner-sharing octahedral tilt angles are 43°. In the second S site, S(2) is bonded in a 1-coordinate geometry to one Ba(1), one Ba(2), one Pb(1), and one Ge(2) atom. In the third S site, S(3) is bonded to two equivalent Ba(1), two equivalent Ba(2), and one Ge(2) atom to form distorted SBa4Ge square pyramids that share corners with two equivalent S(6)Ba4GePb octahedra, corners with two equivalent S(5)Ba4Ge square pyramids, corners with two equivalent Br(1)Ba4Pb square pyramids, corners with four equivalent S(1)Ba2GePb trigonal pyramids,  an edgeedge with one S(5)Ba4Ge square pyramid,  an edgeedge with one Br(1)Ba4Pb square pyramid, edges with two equivalent S(4)Ba4Ge square pyramids, and  a faceface with one S(6)Ba4GePb octahedra. The corner-sharing octahedral tilt angles are 39°. In the fourth S site, S(4) is bonded to two equivalent Ba(1), two equivalent Ba(2), and one Ge(1) atom to form distorted SBa4Ge square pyramids that share corners with two equivalent S(6)Ba4GePb octahedra, corners with two equivalent S(5)Ba4Ge square pyramids, corners with two equivalent Br(1)Ba4Pb square pyramids, corners with two equivalent S(1)Ba2GePb trigonal pyramids,  an edgeedge with one S(6)Ba4GePb octahedra,  an edgeedge with one Br(1)Ba4Pb square pyramid, edges with two equivalent S(3)Ba4Ge square pyramids, edges with two equivalent S(1)Ba2GePb trigonal pyramids, and  a faceface with one S(5)Ba4Ge square pyramid. The corner-sharing octahedral tilt angles are 58°. In the fifth S site, S(5) is bonded to four equivalent Ba(1) and one Ge(1) atom to form distorted SBa4Ge square pyramids that share corners with two equivalent S(3)Ba4Ge square pyramids, corners with two equivalent S(4)Ba4Ge square pyramids, corners with four equivalent S(5)Ba4Ge square pyramids, corners with two equivalent S(1)Ba2GePb trigonal pyramids,  an edgeedge with one S(3)Ba4Ge square pyramid, edges with four equivalent Br(1)Ba4Pb square pyramids, edges with two equivalent S(1)Ba2GePb trigonal pyramids, and  a faceface with one S(4)Ba4Ge square pyramid. In the sixth S site, S(6) is bonded to four equivalent Ba(2), one Pb(1), and one Ge(2) atom to form distorted SBa4GePb octahedra that share corners with four equivalent S(6)Ba4GePb octahedra,  a cornercorner with one Br(1)Ba4Pb square pyramid, corners with two equivalent S(3)Ba4Ge square pyramids, corners with two equivalent S(4)Ba4Ge square pyramids, corners with two equivalent S(1)Ba2GePb trigonal pyramids,  an edgeedge with one S(4)Ba4Ge square pyramid, edges with two equivalent S(1)Ba2GePb trigonal pyramids, and  a faceface with one S(3)Ba4Ge square pyramid. The corner-sharing octahedral tilt angles are 32°. There are two inequivalent Br sites. In the first Br site, Br(1) is bonded to four equivalent Ba(1) and one Pb(1) atom to form BrBa4Pb square pyramids that share  a cornercorner with one S(6)Ba4GePb octahedra, corners with two equivalent S(3)Ba4Ge square pyramids, corners with two equivalent S(4)Ba4Ge square pyramids, corners with four equivalent Br(1)Ba4Pb square pyramids, corners with two equivalent S(1)Ba2GePb trigonal pyramids,  an edgeedge with one S(3)Ba4Ge square pyramid,  an edgeedge with one S(4)Ba4Ge square pyramid, edges with four equivalent S(5)Ba4Ge square pyramids, and edges with two equivalent S(1)Ba2GePb trigonal pyramids. The corner-sharing octahedral tilt angles are 12°. In the second Br site, Br(2) is bonded in a square co-planar geometry to four equivalent Ba(2) atoms.