Ba3Zr2S7 crystallizes in the orthorhombic Cccm space group. There are two inequivalent Ba sites. In the first Ba site, Ba(1) is bonded in a 9-coordinate geometry to two equivalent S(1), two equivalent S(3), and five equivalent S(4) atoms. In the second Ba site, Ba(2) is bonded to four equivalent S(1), four equivalent S(2), and four equivalent S(3) atoms to form BaS12 cuboctahedra that share corners with four equivalent Ba(2)S12 cuboctahedra, faces with four equivalent Ba(2)S12 cuboctahedra, and faces with eight equivalent Zr(1)S6 octahedra. Zr(1) is bonded to one S(2), one S(4), two equivalent S(1), and two equivalent S(3) atoms to form ZrS6 octahedra that share corners with five equivalent Zr(1)S6 octahedra and faces with four equivalent Ba(2)S12 cuboctahedra. The corner-sharing octahedral tilt angles range from 0-7°. There are four inequivalent S sites. In the first 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, face, and corner-sharing SBa4Zr2 octahedra. The corner-sharing octahedral tilt angles range from 0-61°. In the second S site, S(2) is bonded to four equivalent Ba(2) and two equivalent Zr(1) atoms to form a mixture of distorted edge, face, and corner-sharing SBa4Zr2 octahedra. The corner-sharing octahedral tilt angles range from 0-60°. In the third S site, S(3) is bonded to two equivalent Ba(1), two equivalent Ba(2), and two equivalent Zr(1) atoms to form a mixture of distorted edge, face, and corner-sharing SBa4Zr2 octahedra. The corner-sharing octahedral tilt angles range from 0-61°. In the fourth S site, S(4) is bonded in a 6-coordinate geometry to five equivalent Ba(1) and one Zr(1) atom.
Ba3Zr2S7 crystallizes in the orthorhombic Cccm space group. There are two inequivalent Ba sites. In the first Ba site, Ba(1) is bonded in a 9-coordinate geometry to two equivalent S(1), two equivalent S(3), and five equivalent S(4) atoms. Both Ba(1)-S(1) bond lengths are 3.35 Å. Both Ba(1)-S(3) bond lengths are 3.32 Å. There are a spread of Ba(1)-S(4) bond distances ranging from 3.13-3.81 Å. In the second Ba site, Ba(2) is bonded to four equivalent S(1), four equivalent S(2), and four equivalent S(3) atoms to form BaS12 cuboctahedra that share corners with four equivalent Ba(2)S12 cuboctahedra, faces with four equivalent Ba(2)S12 cuboctahedra, and faces with eight equivalent Zr(1)S6 octahedra. All Ba(2)-S(1) bond lengths are 3.58 Å. There are two shorter (3.56 Å) and two longer (3.57 Å) Ba(2)-S(2) bond lengths. All Ba(2)-S(3) bond lengths are 3.51 Å. Zr(1) is bonded to one S(2), one S(4), two equivalent S(1), and two equivalent S(3) atoms to form ZrS6 octahedra that share corners with five equivalent Zr(1)S6 octahedra and faces with four equivalent Ba(2)S12 cuboctahedra. The corner-sharing octahedral tilt angles range from 0-7°. The Zr(1)-S(2) bond length is 2.59 Å. The Zr(1)-S(4) bond length is 2.53 Å. Both Zr(1)-S(1) bond lengths are 2.52 Å. Both Zr(1)-S(3) bond lengths are 2.53 Å. There are four inequivalent S sites. In the first 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, face, and corner-sharing SBa4Zr2 octahedra. The corner-sharing octahedral tilt angles range from 0-61°. In the second S site, S(2) is bonded to four equivalent Ba(2) and two equivalent Zr(1) atoms to form a mixture of distorted edge, face, and corner-sharing SBa4Zr2 octahedra. The corner-sharing octahedral tilt angles range from 0-60°. In the third S site, S(3) is bonded to two equivalent Ba(1), two equivalent Ba(2), and two equivalent Zr(1) atoms to form a mixture of distorted edge, face, and corner-sharing SBa4Zr2 octahedra. The corner-sharing octahedral tilt angles range from 0-61°. In the fourth S site, S(4) is bonded in a 6-coordinate geometry to five equivalent Ba(1) and one Zr(1) atom.