Cr5S8 is beta indium sulfide-like structured and crystallizes in the monoclinic Cm space group. There are eight inequivalent Cr sites. In the first Cr site, Cr(1) is bonded to one S(1), one S(12), two equivalent S(10), and two equivalent S(11) atoms to form a mixture of face and corner-sharing CrS6 octahedra. The corner-sharing octahedral tilt angles range from 48-53°. In the second Cr site, Cr(2) is bonded to one S(4), one S(5), two equivalent S(8), and two equivalent S(9) atoms to form a mixture of face and corner-sharing CrS6 octahedra. The corner-sharing octahedral tilt angles range from 48-53°. In the third Cr site, Cr(3) is bonded to one S(12), one S(3), two equivalent S(11), and two equivalent S(8) atoms to form a mixture of edge, face, and corner-sharing CrS6 octahedra. The corner-sharing octahedral tilt angles are 53°. In the fourth Cr site, Cr(4) is bonded to one S(1), one S(2), two equivalent S(10), and two equivalent S(9) atoms to form a mixture of edge, face, and corner-sharing CrS6 octahedra. The corner-sharing octahedral tilt angles are 53°. In the fifth Cr site, Cr(5) is bonded to one S(4), one S(7), two equivalent S(11), and two equivalent S(8) atoms to form a mixture of edge, face, and corner-sharing CrS6 octahedra. The corner-sharing octahedral tilt angles are 53°. In the sixth Cr site, Cr(6) is bonded to one S(5), one S(6), two equivalent S(10), and two equivalent S(9) atoms to form a mixture of edge, face, and corner-sharing CrS6 octahedra. The corner-sharing octahedral tilt angles are 51°. In the seventh Cr site, Cr(7) is bonded to one S(11), one S(12), one S(3), one S(4), one S(7), and one S(8) atom to form a mixture of edge and corner-sharing CrS6 octahedra. The corner-sharing octahedral tilt angles range from 48-51°. In the eighth Cr site, Cr(8) is bonded to one S(1), one S(10), one S(2), one S(5), one S(6), and one S(9) atom to form a mixture of edge and corner-sharing CrS6 octahedra. The corner-sharing octahedral tilt angles range from 48-52°. There are twelve inequivalent S sites. In the first S site, S(1) is bonded to one Cr(1), one Cr(4), and two equivalent Cr(8) atoms to form a mixture of edge and corner-sharing SCr4 trigonal pyramids. In the second S site, S(2) is bonded in a distorted T-shaped geometry to one Cr(4) and two equivalent Cr(8) atoms. In the third S site, S(3) is bonded in a distorted T-shaped geometry to one Cr(3) and two equivalent Cr(7) atoms. In the fourth S site, S(4) is bonded to one Cr(2), one Cr(5), and two equivalent Cr(7) atoms to form a mixture of edge and corner-sharing SCr4 trigonal pyramids. In the fifth S site, S(5) is bonded to one Cr(2), one Cr(6), and two equivalent Cr(8) atoms to form a mixture of edge and corner-sharing SCr4 trigonal pyramids. In the sixth S site, S(6) is bonded in a distorted T-shaped geometry to one Cr(6) and two equivalent Cr(8) atoms. In the seventh S site, S(7) is bonded in a distorted T-shaped geometry to one Cr(5) and two equivalent Cr(7) atoms. In the eighth S site, S(8) is bonded in a rectangular see-saw-like geometry to one Cr(2), one Cr(3), one Cr(5), and one Cr(7) atom. In the ninth S site, S(9) is bonded in a rectangular see-saw-like geometry to one Cr(2), one Cr(4), one Cr(6), and one Cr(8) atom. In the tenth S site, S(10) is bonded in a rectangular see-saw-like geometry to one Cr(1), one Cr(4), one Cr(6), and one Cr(8) atom. In the eleventh S site, S(11) is bonded in a rectangular see-saw-like geometry to one Cr(1), one Cr(3), one Cr(5), and one Cr(7) atom. In the twelfth S site, S(12) is bonded to one Cr(1), one Cr(3), and two equivalent Cr(7) atoms to form a mixture of edge and corner-sharing SCr4 trigonal pyramids.
Cr5S8 is beta indium sulfide-like structured and crystallizes in the monoclinic Cm space group. There are eight inequivalent Cr sites. In the first Cr site, Cr(1) is bonded to one S(1), one S(12), two equivalent S(10), and two equivalent S(11) atoms to form a mixture of face and corner-sharing CrS6 octahedra. The corner-sharing octahedral tilt angles range from 48-53°. The Cr(1)-S(1) bond length is 2.46 Å. The Cr(1)-S(12) bond length is 2.44 Å. Both Cr(1)-S(10) bond lengths are 2.41 Å. Both Cr(1)-S(11) bond lengths are 2.39 Å. In the second Cr site, Cr(2) is bonded to one S(4), one S(5), two equivalent S(8), and two equivalent S(9) atoms to form a mixture of face and corner-sharing CrS6 octahedra. The corner-sharing octahedral tilt angles range from 48-53°. The Cr(2)-S(4) bond length is 2.46 Å. The Cr(2)-S(5) bond length is 2.44 Å. Both Cr(2)-S(8) bond lengths are 2.41 Å. Both Cr(2)-S(9) bond lengths are 2.39 Å. In the third Cr site, Cr(3) is bonded to one S(12), one S(3), two equivalent S(11), and two equivalent S(8) atoms to form a mixture of edge, face, and corner-sharing CrS6 octahedra. The corner-sharing octahedral tilt angles are 53°. The Cr(3)-S(12) bond length is 2.44 Å. The Cr(3)-S(3) bond length is 2.33 Å. Both Cr(3)-S(11) bond lengths are 2.41 Å. Both Cr(3)-S(8) bond lengths are 2.38 Å. In the fourth Cr site, Cr(4) is bonded to one S(1), one S(2), two equivalent S(10), and two equivalent S(9) atoms to form a mixture of edge, face, and corner-sharing CrS6 octahedra. The corner-sharing octahedral tilt angles are 53°. The Cr(4)-S(1) bond length is 2.43 Å. The Cr(4)-S(2) bond length is 2.33 Å. Both Cr(4)-S(10) bond lengths are 2.41 Å. Both Cr(4)-S(9) bond lengths are 2.38 Å. In the fifth Cr site, Cr(5) is bonded to one S(4), one S(7), two equivalent S(11), and two equivalent S(8) atoms to form a mixture of edge, face, and corner-sharing CrS6 octahedra. The corner-sharing octahedral tilt angles are 53°. The Cr(5)-S(4) bond length is 2.44 Å. The Cr(5)-S(7) bond length is 2.33 Å. Both Cr(5)-S(11) bond lengths are 2.38 Å. Both Cr(5)-S(8) bond lengths are 2.40 Å. In the sixth Cr site, Cr(6) is bonded to one S(5), one S(6), two equivalent S(10), and two equivalent S(9) atoms to form a mixture of edge, face, and corner-sharing CrS6 octahedra. The corner-sharing octahedral tilt angles are 51°. The Cr(6)-S(5) bond length is 2.38 Å. The Cr(6)-S(6) bond length is 2.33 Å. Both Cr(6)-S(10) bond lengths are 2.38 Å. Both Cr(6)-S(9) bond lengths are 2.41 Å. In the seventh Cr site, Cr(7) is bonded to one S(11), one S(12), one S(3), one S(4), one S(7), and one S(8) atom to form a mixture of edge and corner-sharing CrS6 octahedra. The corner-sharing octahedral tilt angles range from 48-51°. The Cr(7)-S(11) bond length is 2.41 Å. The Cr(7)-S(12) bond length is 2.44 Å. The Cr(7)-S(3) bond length is 2.31 Å. The Cr(7)-S(4) bond length is 2.45 Å. The Cr(7)-S(7) bond length is 2.31 Å. The Cr(7)-S(8) bond length is 2.42 Å. In the eighth Cr site, Cr(8) is bonded to one S(1), one S(10), one S(2), one S(5), one S(6), and one S(9) atom to form a mixture of edge and corner-sharing CrS6 octahedra. The corner-sharing octahedral tilt angles range from 48-52°. The Cr(8)-S(1) bond length is 2.47 Å. The Cr(8)-S(10) bond length is 2.40 Å. The Cr(8)-S(2) bond length is 2.30 Å. The Cr(8)-S(5) bond length is 2.43 Å. The Cr(8)-S(6) bond length is 2.31 Å. The Cr(8)-S(9) bond length is 2.40 Å. There are twelve inequivalent S sites. In the first S site, S(1) is bonded to one Cr(1), one Cr(4), and two equivalent Cr(8) atoms to form a mixture of edge and corner-sharing SCr4 trigonal pyramids. In the second S site, S(2) is bonded in a distorted T-shaped geometry to one Cr(4) and two equivalent Cr(8) atoms. In the third S site, S(3) is bonded in a distorted T-shaped geometry to one Cr(3) and two equivalent Cr(7) atoms. In the fourth S site, S(4) is bonded to one Cr(2), one Cr(5), and two equivalent Cr(7) atoms to form a mixture of edge and corner-sharing SCr4 trigonal pyramids. In the fifth S site, S(5) is bonded to one Cr(2), one Cr(6), and two equivalent Cr(8) atoms to form a mixture of edge and corner-sharing SCr4 trigonal pyramids. In the sixth S site, S(6) is bonded in a distorted T-shaped geometry to one Cr(6) and two equivalent Cr(8) atoms. In the seventh S site, S(7) is bonded in a distorted T-shaped geometry to one Cr(5) and two equivalent Cr(7) atoms. In the eighth S site, S(8) is bonded in a rectangular see-saw-like geometry to one Cr(2), one Cr(3), one Cr(5), and one Cr(7) atom. In the ninth S site, S(9) is bonded in a rectangular see-saw-like geometry to one Cr(2), one Cr(4), one Cr(6), and one Cr(8) atom. In the tenth S site, S(10) is bonded in a rectangular see-saw-like geometry to one Cr(1), one Cr(4), one Cr(6), and one Cr(8) atom. In the eleventh S site, S(11) is bonded in a rectangular see-saw-like geometry to one Cr(1), one Cr(3), one Cr(5), and one Cr(7) atom. In the twelfth S site, S(12) is bonded to one Cr(1), one Cr(3), and two equivalent Cr(7) atoms to form a mixture of edge and corner-sharing SCr4 trigonal pyramids.