Ba4CoNi3S8 crystallizes in the orthorhombic Amm2 space group. There are three inequivalent Ba sites. In the first Ba site, Ba(1) is bonded in a 5-coordinate geometry to one S(5) and four equivalent S(6) atoms. In the second Ba site, Ba(2) is bonded in a 5-coordinate geometry to one S(4) and four equivalent S(6) atoms. In the third Ba site, Ba(3) is bonded in a 5-coordinate geometry to one S(6), two equivalent S(4), and two equivalent S(5) atoms. Co(1) is bonded in a 5-coordinate geometry to one S(5), two equivalent S(1), and two equivalent S(3) atoms. There are two inequivalent Ni sites. In the first Ni site, Ni(1) is bonded in a 5-coordinate geometry to one S(4), two equivalent S(1), and two equivalent S(2) atoms. In the second Ni site, Ni(2) is bonded in a 5-coordinate geometry to one S(2), one S(3), one S(6), and two equivalent S(1) atoms. There are six inequivalent S sites. In the first S site, S(1) is bonded in a 4-coordinate geometry to one Co(1), one Ni(1), and two equivalent Ni(2) atoms. In the second S site, S(2) is bonded in a 4-coordinate geometry to two equivalent Ni(1) and two equivalent Ni(2) atoms. In the third S site, S(3) is bonded in a 4-coordinate geometry to two equivalent Co(1) and two equivalent Ni(2) atoms. In the fourth S site, S(4) is bonded to one Ba(2), four equivalent Ba(3), and one Ni(1) atom to form SBa5Ni octahedra that share corners with four equivalent S(5)Ba5Co octahedra, edges with two equivalent S(5)Ba5Co octahedra, edges with two equivalent S(4)Ba5Ni octahedra, and edges with four equivalent S(6)Ba5Ni octahedra. The corner-sharing octahedral tilt angles are 13°. In the fifth S site, S(5) is bonded to one Ba(1), four equivalent Ba(3), and one Co(1) atom to form SBa5Co octahedra that share corners with four equivalent S(4)Ba5Ni octahedra, edges with two equivalent S(5)Ba5Co octahedra, edges with two equivalent S(4)Ba5Ni octahedra, and edges with four equivalent S(6)Ba5Ni octahedra. The corner-sharing octahedral tilt angles are 13°. In the sixth S site, S(6) is bonded to one Ba(3), two equivalent Ba(1), two equivalent Ba(2), and one Ni(2) atom to form SBa5Ni octahedra that share corners with four equivalent S(6)Ba5Ni octahedra, edges with two equivalent S(5)Ba5Co octahedra, edges with two equivalent S(4)Ba5Ni octahedra, and edges with four equivalent S(6)Ba5Ni octahedra. The corner-sharing octahedral tilt angles range from 13-14°.
Ba4CoNi3S8 crystallizes in the orthorhombic Amm2 space group. There are three inequivalent Ba sites. In the first Ba site, Ba(1) is bonded in a 5-coordinate geometry to one S(5) and four equivalent S(6) atoms. The Ba(1)-S(5) bond length is 3.26 Å. All Ba(1)-S(6) bond lengths are 3.16 Å. In the second Ba site, Ba(2) is bonded in a 5-coordinate geometry to one S(4) and four equivalent S(6) atoms. The Ba(2)-S(4) bond length is 3.19 Å. All Ba(2)-S(6) bond lengths are 3.16 Å. In the third Ba site, Ba(3) is bonded in a 5-coordinate geometry to one S(6), two equivalent S(4), and two equivalent S(5) atoms. The Ba(3)-S(6) bond length is 3.20 Å. Both Ba(3)-S(4) bond lengths are 3.14 Å. Both Ba(3)-S(5) bond lengths are 3.17 Å. Co(1) is bonded in a 5-coordinate geometry to one S(5), two equivalent S(1), and two equivalent S(3) atoms. The Co(1)-S(5) bond length is 2.27 Å. Both Co(1)-S(1) bond lengths are 2.29 Å. Both Co(1)-S(3) bond lengths are 2.34 Å. There are two inequivalent Ni sites. In the first Ni site, Ni(1) is bonded in a 5-coordinate geometry to one S(4), two equivalent S(1), and two equivalent S(2) atoms. The Ni(1)-S(4) bond length is 2.31 Å. Both Ni(1)-S(1) bond lengths are 2.40 Å. Both Ni(1)-S(2) bond lengths are 2.35 Å. In the second Ni site, Ni(2) is bonded in a 5-coordinate geometry to one S(2), one S(3), one S(6), and two equivalent S(1) atoms. The Ni(2)-S(2) bond length is 2.35 Å. The Ni(2)-S(3) bond length is 2.34 Å. The Ni(2)-S(6) bond length is 2.33 Å. Both Ni(2)-S(1) bond lengths are 2.35 Å. There are six inequivalent S sites. In the first S site, S(1) is bonded in a 4-coordinate geometry to one Co(1), one Ni(1), and two equivalent Ni(2) atoms. In the second S site, S(2) is bonded in a 4-coordinate geometry to two equivalent Ni(1) and two equivalent Ni(2) atoms. In the third S site, S(3) is bonded in a 4-coordinate geometry to two equivalent Co(1) and two equivalent Ni(2) atoms. In the fourth S site, S(4) is bonded to one Ba(2), four equivalent Ba(3), and one Ni(1) atom to form SBa5Ni octahedra that share corners with four equivalent S(5)Ba5Co octahedra, edges with two equivalent S(5)Ba5Co octahedra, edges with two equivalent S(4)Ba5Ni octahedra, and edges with four equivalent S(6)Ba5Ni octahedra. The corner-sharing octahedral tilt angles are 13°. In the fifth S site, S(5) is bonded to one Ba(1), four equivalent Ba(3), and one Co(1) atom to form SBa5Co octahedra that share corners with four equivalent S(4)Ba5Ni octahedra, edges with two equivalent S(5)Ba5Co octahedra, edges with two equivalent S(4)Ba5Ni octahedra, and edges with four equivalent S(6)Ba5Ni octahedra. The corner-sharing octahedral tilt angles are 13°. In the sixth S site, S(6) is bonded to one Ba(3), two equivalent Ba(1), two equivalent Ba(2), and one Ni(2) atom to form SBa5Ni octahedra that share corners with four equivalent S(6)Ba5Ni octahedra, edges with two equivalent S(5)Ba5Co octahedra, edges with two equivalent S(4)Ba5Ni octahedra, and edges with four equivalent S(6)Ba5Ni octahedra. The corner-sharing octahedral tilt angles range from 13-14°.