Ba3Zr2S7 crystallizes in the tetragonal P4_2/mnm space group. There are two inequivalent Ba sites. In the first Ba site, Ba(1) is bonded in a 12-coordinate geometry to two equivalent S(2), two equivalent S(4), four equivalent S(1), and four equivalent S(5) atoms. In the second Ba site, Ba(2) is bonded in a 7-coordinate geometry to one S(2), one S(4), two equivalent S(1), and three equivalent S(3) atoms. Zr(1) is bonded to one S(2), one S(3), one S(4), one S(5), and two equivalent S(1) atoms to form corner-sharing ZrS6 octahedra. The corner-sharing octahedral tilt angles range from 5-19°. There are five inequivalent S sites. In the first S site, S(3) is bonded in a distorted rectangular see-saw-like geometry to three equivalent Ba(2) and one Zr(1) atom. In the second S site, S(4) is bonded to two equivalent Ba(1), two equivalent Ba(2), and two equivalent Zr(1) atoms to form a mixture of distorted edge, corner, and face-sharing SBa4Zr2 octahedra. The corner-sharing octahedral tilt angles are 64°. In the third S site, S(5) is bonded in a 4-coordinate geometry to four equivalent Ba(1) and two equivalent Zr(1) atoms. In the fourth S site, S(1) is bonded to two equivalent Ba(1), two equivalent Ba(2), and two equivalent Zr(1) atoms to form a mixture of distorted edge, corner, and face-sharing SBa4Zr2 octahedra. The corner-sharing octahedral tilt angles range from 1-64°. In the fifth S site, S(2) is bonded in a 4-coordinate geometry to two equivalent Ba(1), two equivalent Ba(2), and two equivalent Zr(1) atoms.
Ba3Zr2S7 crystallizes in the tetragonal P4_2/mnm space group. There are two inequivalent Ba sites. In the first Ba site, Ba(1) is bonded in a 12-coordinate geometry to two equivalent S(2), two equivalent S(4), four equivalent S(1), and four equivalent S(5) atoms. Both Ba(1)-S(2) bond lengths are 3.76 Å. Both Ba(1)-S(4) bond lengths are 3.32 Å. All Ba(1)-S(1) bond lengths are 3.51 Å. There are two shorter (3.27 Å) and two longer (3.88 Å) Ba(1)-S(5) bond lengths. In the second Ba site, Ba(2) is bonded in a 7-coordinate geometry to one S(2), one S(4), two equivalent S(1), and three equivalent S(3) atoms. The Ba(2)-S(2) bond length is 3.21 Å. The Ba(2)-S(4) bond length is 3.48 Å. Both Ba(2)-S(1) bond lengths are 3.35 Å. There is one shorter (3.13 Å) and two longer (3.28 Å) Ba(2)-S(3) bond lengths. Zr(1) is bonded to one S(2), one S(3), one S(4), one S(5), and two equivalent S(1) atoms to form corner-sharing ZrS6 octahedra. The corner-sharing octahedral tilt angles range from 5-19°. The Zr(1)-S(2) bond length is 2.53 Å. The Zr(1)-S(3) bond length is 2.53 Å. The Zr(1)-S(4) bond length is 2.56 Å. The Zr(1)-S(5) bond length is 2.58 Å. Both Zr(1)-S(1) bond lengths are 2.52 Å. There are five inequivalent S sites. In the first S site, S(3) is bonded in a distorted rectangular see-saw-like geometry to three equivalent Ba(2) and one Zr(1) atom. In the second S site, S(4) is bonded to two equivalent Ba(1), two equivalent Ba(2), and two equivalent Zr(1) atoms to form a mixture of distorted edge, corner, and face-sharing SBa4Zr2 octahedra. The corner-sharing octahedral tilt angles are 64°. In the third S site, S(5) is bonded in a 4-coordinate geometry to four equivalent Ba(1) and two equivalent Zr(1) atoms. In the fourth S site, S(1) is bonded to two equivalent Ba(1), two equivalent Ba(2), and two equivalent Zr(1) atoms to form a mixture of distorted edge, corner, and face-sharing SBa4Zr2 octahedra. The corner-sharing octahedral tilt angles range from 1-64°. In the fifth S site, S(2) is bonded in a 4-coordinate geometry to two equivalent Ba(1), two equivalent Ba(2), and two equivalent Zr(1) atoms.