Ba4GeSiS8 crystallizes in the orthorhombic Pmc2_1 space group. There are four inequivalent Ba sites. In the first Ba site, Ba(1) is bonded in a 8-coordinate geometry to one S(3), one S(5), two equivalent S(1), two equivalent S(2), and two equivalent S(4) atoms. In the second Ba site, Ba(2) is bonded in a 8-coordinate geometry to one S(4), one S(6), two equivalent S(1), two equivalent S(2), and two equivalent S(3) atoms. In the third Ba site, Ba(3) is bonded in a 9-coordinate geometry to one S(5), two equivalent S(3), two equivalent S(6), and four equivalent S(1) atoms. In the fourth Ba site, Ba(4) is bonded in a 9-coordinate geometry to one S(6), two equivalent S(4), two equivalent S(5), and four equivalent S(2) atoms. Ge(1) is bonded in a tetrahedral geometry to one S(3), one S(5), and two equivalent S(2) atoms. Si(1) is bonded in a tetrahedral geometry to one S(4), one S(6), and two equivalent S(1) atoms. There are six inequivalent S sites. In the first S site, S(1) is bonded to one Ba(1), one Ba(2), two equivalent Ba(3), and one Si(1) atom to form distorted SBa4Si square pyramids that share corners with four equivalent S(1)Ba4Si square pyramids,  a cornercorner with one S(5)Ba4Ge trigonal bipyramid, corners with two equivalent S(2)Ba4Ge trigonal bipyramids, corners with four equivalent S(6)Ba4Si trigonal bipyramids,  an edgeedge with one S(1)Ba4Si square pyramid,  an edgeedge with one S(2)Ba4Ge trigonal bipyramid,  an edgeedge with one S(5)Ba4Ge trigonal bipyramid,  an edgeedge with one S(6)Ba4Si trigonal bipyramid, and  a faceface with one S(1)Ba4Si square pyramid. In the second S site, S(2) is bonded to one Ba(1), one Ba(2), two equivalent Ba(4), and one Ge(1) atom to form distorted SBa4Ge trigonal bipyramids that share corners with two equivalent S(1)Ba4Si square pyramids,  a cornercorner with one S(6)Ba4Si trigonal bipyramid, corners with four equivalent S(2)Ba4Ge trigonal bipyramids, corners with four equivalent S(5)Ba4Ge trigonal bipyramids,  an edgeedge with one S(1)Ba4Si square pyramid,  an edgeedge with one S(2)Ba4Ge trigonal bipyramid,  an edgeedge with one S(5)Ba4Ge trigonal bipyramid,  an edgeedge with one S(6)Ba4Si trigonal bipyramid, and  a faceface with one S(2)Ba4Ge trigonal bipyramid. In the third S site, S(3) is bonded in a 6-coordinate geometry to one Ba(1), two equivalent Ba(2), two equivalent Ba(3), and one Ge(1) atom. In the fourth S site, S(4) is bonded in a 6-coordinate geometry to one Ba(2), two equivalent Ba(1), two equivalent Ba(4), and one Si(1) atom. In the fifth S site, S(5) is bonded to one Ba(1), one Ba(3), two equivalent Ba(4), and one Ge(1) atom to form distorted SBa4Ge trigonal bipyramids that share corners with two equivalent S(1)Ba4Si square pyramids, corners with two equivalent S(5)Ba4Ge trigonal bipyramids, corners with eight equivalent S(2)Ba4Ge trigonal bipyramids, edges with two equivalent S(1)Ba4Si square pyramids, edges with two equivalent S(2)Ba4Ge trigonal bipyramids, and edges with two equivalent S(6)Ba4Si trigonal bipyramids. In the sixth S site, S(6) is bonded to one Ba(2), one Ba(4), two equivalent Ba(3), and one Si(1) atom to form distorted SBa4Si trigonal bipyramids that share corners with eight equivalent S(1)Ba4Si square pyramids, corners with two equivalent S(2)Ba4Ge trigonal bipyramids, corners with two equivalent S(6)Ba4Si trigonal bipyramids, edges with two equivalent S(1)Ba4Si square pyramids, edges with two equivalent S(2)Ba4Ge trigonal bipyramids, and edges with two equivalent S(5)Ba4Ge trigonal bipyramids.
Ba4GeSiS8 crystallizes in the orthorhombic Pmc2_1 space group. There are four inequivalent Ba sites. In the first Ba site, Ba(1) is bonded in a 8-coordinate geometry to one S(3), one S(5), two equivalent S(1), two equivalent S(2), and two equivalent S(4) atoms. The Ba(1)-S(3) bond length is 3.59 Å. The Ba(1)-S(5) bond length is 3.27 Å. Both Ba(1)-S(1) bond lengths are 3.26 Å. Both Ba(1)-S(2) bond lengths are 3.37 Å. Both Ba(1)-S(4) bond lengths are 3.49 Å. In the second Ba site, Ba(2) is bonded in a 8-coordinate geometry to one S(4), one S(6), two equivalent S(1), two equivalent S(2), and two equivalent S(3) atoms. The Ba(2)-S(4) bond length is 3.62 Å. The Ba(2)-S(6) bond length is 3.34 Å. Both Ba(2)-S(1) bond lengths are 3.36 Å. Both Ba(2)-S(2) bond lengths are 3.28 Å. Both Ba(2)-S(3) bond lengths are 3.48 Å. In the third Ba site, Ba(3) is bonded in a 9-coordinate geometry to one S(5), two equivalent S(3), two equivalent S(6), and four equivalent S(1) atoms. The Ba(3)-S(5) bond length is 3.33 Å. There is one shorter (3.13 Å) and one longer (3.33 Å) Ba(3)-S(3) bond length. Both Ba(3)-S(6) bond lengths are 3.56 Å. There are two shorter (3.25 Å) and two longer (3.37 Å) Ba(3)-S(1) bond lengths. In the fourth Ba site, Ba(4) is bonded in a 9-coordinate geometry to one S(6), two equivalent S(4), two equivalent S(5), and four equivalent S(2) atoms. The Ba(4)-S(6) bond length is 3.29 Å. There is one shorter (3.11 Å) and one longer (3.43 Å) Ba(4)-S(4) bond length. Both Ba(4)-S(5) bond lengths are 3.55 Å. There are two shorter (3.25 Å) and two longer (3.32 Å) Ba(4)-S(2) bond lengths. Ge(1) is bonded in a tetrahedral geometry to one S(3), one S(5), and two equivalent S(2) atoms. The Ge(1)-S(3) bond length is 2.24 Å. The Ge(1)-S(5) bond length is 2.22 Å. Both Ge(1)-S(2) bond lengths are 2.20 Å. Si(1) is bonded in a tetrahedral geometry to one S(4), one S(6), and two equivalent S(1) atoms. The Si(1)-S(4) bond length is 2.14 Å. The Si(1)-S(6) bond length is 2.14 Å. Both Si(1)-S(1) bond lengths are 2.12 Å. There are six inequivalent S sites. In the first S site, S(1) is bonded to one Ba(1), one Ba(2), two equivalent Ba(3), and one Si(1) atom to form distorted SBa4Si square pyramids that share corners with four equivalent S(1)Ba4Si square pyramids,  a cornercorner with one S(5)Ba4Ge trigonal bipyramid, corners with two equivalent S(2)Ba4Ge trigonal bipyramids, corners with four equivalent S(6)Ba4Si trigonal bipyramids,  an edgeedge with one S(1)Ba4Si square pyramid,  an edgeedge with one S(2)Ba4Ge trigonal bipyramid,  an edgeedge with one S(5)Ba4Ge trigonal bipyramid,  an edgeedge with one S(6)Ba4Si trigonal bipyramid, and  a faceface with one S(1)Ba4Si square pyramid. In the second S site, S(2) is bonded to one Ba(1), one Ba(2), two equivalent Ba(4), and one Ge(1) atom to form distorted SBa4Ge trigonal bipyramids that share corners with two equivalent S(1)Ba4Si square pyramids,  a cornercorner with one S(6)Ba4Si trigonal bipyramid, corners with four equivalent S(2)Ba4Ge trigonal bipyramids, corners with four equivalent S(5)Ba4Ge trigonal bipyramids,  an edgeedge with one S(1)Ba4Si square pyramid,  an edgeedge with one S(2)Ba4Ge trigonal bipyramid,  an edgeedge with one S(5)Ba4Ge trigonal bipyramid,  an edgeedge with one S(6)Ba4Si trigonal bipyramid, and  a faceface with one S(2)Ba4Ge trigonal bipyramid. In the third S site, S(3) is bonded in a 6-coordinate geometry to one Ba(1), two equivalent Ba(2), two equivalent Ba(3), and one Ge(1) atom. In the fourth S site, S(4) is bonded in a 6-coordinate geometry to one Ba(2), two equivalent Ba(1), two equivalent Ba(4), and one Si(1) atom. In the fifth S site, S(5) is bonded to one Ba(1), one Ba(3), two equivalent Ba(4), and one Ge(1) atom to form distorted SBa4Ge trigonal bipyramids that share corners with two equivalent S(1)Ba4Si square pyramids, corners with two equivalent S(5)Ba4Ge trigonal bipyramids, corners with eight equivalent S(2)Ba4Ge trigonal bipyramids, edges with two equivalent S(1)Ba4Si square pyramids, edges with two equivalent S(2)Ba4Ge trigonal bipyramids, and edges with two equivalent S(6)Ba4Si trigonal bipyramids. In the sixth S site, S(6) is bonded to one Ba(2), one Ba(4), two equivalent Ba(3), and one Si(1) atom to form distorted SBa4Si trigonal bipyramids that share corners with eight equivalent S(1)Ba4Si square pyramids, corners with two equivalent S(2)Ba4Ge trigonal bipyramids, corners with two equivalent S(6)Ba4Si trigonal bipyramids, edges with two equivalent S(1)Ba4Si square pyramids, edges with two equivalent S(2)Ba4Ge trigonal bipyramids, and edges with two equivalent S(5)Ba4Ge trigonal bipyramids.