Ba2ZnGe2S6O crystallizes in the tetragonal P-42_1m space group. Ba(1) is bonded in a 8-coordinate geometry to three equivalent S(2), four equivalent S(1), and one O(1) atom. Zn(1) is bonded to four equivalent S(1) atoms to form ZnS4 tetrahedra that share corners with four equivalent Ge(1)S3O tetrahedra. Ge(1) is bonded to one S(2), two equivalent S(1), and one O(1) atom to form distorted GeS3O tetrahedra that share  a cornercorner with one Ge(1)S3O tetrahedra and corners with two equivalent Zn(1)S4 tetrahedra. There are two inequivalent S sites. In the first S site, S(1) is bonded to two equivalent Ba(1), one Zn(1), and one Ge(1) atom to form distorted SBa2ZnGe trigonal pyramids that share corners with five equivalent S(2)Ba3Ge tetrahedra, corners with eight equivalent S(1)Ba2ZnGe trigonal pyramids,  an edgeedge with one S(2)Ba3Ge tetrahedra, and  an edgeedge with one S(1)Ba2ZnGe trigonal pyramid. In the second S site, S(2) is bonded to three equivalent Ba(1) and one Ge(1) atom to form distorted SBa3Ge tetrahedra that share corners with four equivalent S(2)Ba3Ge tetrahedra, corners with ten equivalent S(1)Ba2ZnGe trigonal pyramids,  an edgeedge with one S(2)Ba3Ge tetrahedra, and edges with two equivalent S(1)Ba2ZnGe trigonal pyramids. O(1) is bonded in a 4-coordinate geometry to two equivalent Ba(1) and two equivalent Ge(1) atoms.
Ba2ZnGe2S6O crystallizes in the tetragonal P-42_1m space group. Ba(1) is bonded in a 8-coordinate geometry to three equivalent S(2), four equivalent S(1), and one O(1) atom. There is one shorter (3.22 Å) and two longer (3.26 Å) Ba(1)-S(2) bond lengths. There are two shorter (3.22 Å) and two longer (3.24 Å) Ba(1)-S(1) bond lengths. The Ba(1)-O(1) bond length is 3.07 Å. Zn(1) is bonded to four equivalent S(1) atoms to form ZnS4 tetrahedra that share corners with four equivalent Ge(1)S3O tetrahedra. All Zn(1)-S(1) bond lengths are 2.37 Å. Ge(1) is bonded to one S(2), two equivalent S(1), and one O(1) atom to form distorted GeS3O tetrahedra that share  a cornercorner with one Ge(1)S3O tetrahedra and corners with two equivalent Zn(1)S4 tetrahedra. The Ge(1)-S(2) bond length is 2.17 Å. Both Ge(1)-S(1) bond lengths are 2.25 Å. The Ge(1)-O(1) bond length is 1.87 Å. There are two inequivalent S sites. In the first S site, S(1) is bonded to two equivalent Ba(1), one Zn(1), and one Ge(1) atom to form distorted SBa2ZnGe trigonal pyramids that share corners with five equivalent S(2)Ba3Ge tetrahedra, corners with eight equivalent S(1)Ba2ZnGe trigonal pyramids,  an edgeedge with one S(2)Ba3Ge tetrahedra, and  an edgeedge with one S(1)Ba2ZnGe trigonal pyramid. In the second S site, S(2) is bonded to three equivalent Ba(1) and one Ge(1) atom to form distorted SBa3Ge tetrahedra that share corners with four equivalent S(2)Ba3Ge tetrahedra, corners with ten equivalent S(1)Ba2ZnGe trigonal pyramids,  an edgeedge with one S(2)Ba3Ge tetrahedra, and edges with two equivalent S(1)Ba2ZnGe trigonal pyramids. O(1) is bonded in a 4-coordinate geometry to two equivalent Ba(1) and two equivalent Ge(1) atoms.