Ca5(TiS2)8 crystallizes in the monoclinic C2/m space group. There are four inequivalent Ca sites. In the first Ca site, Ca(1) is bonded to two equivalent S(1) and four equivalent S(5) atoms to form distorted CaS6 octahedra that share corners with four equivalent Ti(2)S6 octahedra, corners with eight equivalent Ti(3)S6 octahedra, edges with four equivalent Ca(4)S6 octahedra, and faces with two equivalent Ti(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 44-48°. In the second Ca site, Ca(2) is bonded to two equivalent S(2) and four equivalent S(6) atoms to form distorted CaS6 octahedra that share corners with four equivalent Ti(2)S6 octahedra, corners with eight equivalent Ti(3)S6 octahedra, edges with two equivalent Ca(3)S6 octahedra, and faces with two equivalent Ti(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 45-49°. In the third Ca site, Ca(3) is bonded to two equivalent S(4) and four equivalent S(6) atoms to form distorted CaS6 octahedra that share corners with four equivalent Ti(1)S6 octahedra, corners with eight equivalent Ti(3)S6 octahedra, edges with two equivalent Ca(2)S6 octahedra, and faces with two equivalent Ti(2)S6 octahedra. The corner-sharing octahedral tilt angles range from 48-53°. In the fourth Ca site, Ca(4) is bonded to two equivalent S(1), two equivalent S(3), and two equivalent S(5) atoms to form distorted CaS6 octahedra that share corners with four equivalent Ti(1)S6 octahedra, corners with four equivalent Ti(2)S6 octahedra, corners with four equivalent Ti(3)S6 octahedra, edges with two equivalent Ca(1)S6 octahedra, edges with two equivalent Ca(4)S6 octahedra, and faces with two equivalent Ti(3)S6 octahedra. The corner-sharing octahedral tilt angles range from 47-50°. There are three inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to one S(1), one S(2), two equivalent S(5), and two equivalent S(6) atoms to form TiS6 octahedra that share corners with two equivalent Ca(3)S6 octahedra, corners with four equivalent Ca(4)S6 octahedra, edges with two equivalent Ti(2)S6 octahedra, edges with four equivalent Ti(3)S6 octahedra,  a faceface with one Ca(1)S6 octahedra, and  a faceface with one Ca(2)S6 octahedra. The corner-sharing octahedral tilt angles range from 48-49°. In the second Ti site, Ti(2) is bonded to one S(3), one S(4), two equivalent S(5), and two equivalent S(6) atoms to form TiS6 octahedra that share corners with two equivalent Ca(1)S6 octahedra, corners with two equivalent Ca(2)S6 octahedra, corners with four equivalent Ca(4)S6 octahedra, edges with two equivalent Ti(1)S6 octahedra, edges with four equivalent Ti(3)S6 octahedra, and  a faceface with one Ca(3)S6 octahedra. The corner-sharing octahedral tilt angles range from 44-50°. In the third Ti site, Ti(3) is bonded to one S(1), one S(2), one S(3), one S(4), one S(5), and one S(6) atom to form TiS6 octahedra that share corners with two equivalent Ca(1)S6 octahedra, corners with two equivalent Ca(2)S6 octahedra, corners with two equivalent Ca(3)S6 octahedra, corners with two equivalent Ca(4)S6 octahedra, edges with two equivalent Ti(1)S6 octahedra, edges with two equivalent Ti(2)S6 octahedra, edges with two equivalent Ti(3)S6 octahedra, and  a faceface with one Ca(4)S6 octahedra. The corner-sharing octahedral tilt angles range from 46-53°. There are six inequivalent S sites. In the first S site, S(1) is bonded to one Ca(1), two equivalent Ca(4), one Ti(1), and two equivalent Ti(3) atoms to form distorted SCa3Ti3 pentagonal pyramids that share corners with three equivalent S(1)Ca3Ti3 pentagonal pyramids, edges with two equivalent S(6)Ca2Ti3 trigonal bipyramids, edges with three equivalent S(3)Ca2Ti3 trigonal bipyramids, edges with six equivalent S(5)Ca2Ti3 trigonal bipyramids, and  an edgeedge with one S(4)CaTi3 trigonal pyramid. In the second S site, S(2) is bonded in a rectangular see-saw-like geometry to one Ca(2), one Ti(1), and two equivalent Ti(3) atoms. In the third S site, S(3) is bonded to two equivalent Ca(4), one Ti(2), and two equivalent Ti(3) atoms to form distorted SCa2Ti3 trigonal bipyramids that share corners with two equivalent S(3)Ca2Ti3 trigonal bipyramids, corners with four equivalent S(5)Ca2Ti3 trigonal bipyramids, corners with three equivalent S(4)CaTi3 trigonal pyramids, edges with three equivalent S(1)Ca3Ti3 pentagonal pyramids, edges with two equivalent S(5)Ca2Ti3 trigonal bipyramids, and edges with two equivalent S(6)Ca2Ti3 trigonal bipyramids. In the fourth S site, S(4) is bonded to one Ca(3), one Ti(2), and two equivalent Ti(3) atoms to form SCaTi3 trigonal pyramids that share corners with three equivalent S(3)Ca2Ti3 trigonal bipyramids, corners with four equivalent S(6)Ca2Ti3 trigonal bipyramids,  a cornercorner with one S(4)CaTi3 trigonal pyramid,  an edgeedge with one S(1)Ca3Ti3 pentagonal pyramid, edges with two equivalent S(5)Ca2Ti3 trigonal bipyramids, and edges with two equivalent S(6)Ca2Ti3 trigonal bipyramids. In the fifth S site, S(5) is bonded to one Ca(1), one Ca(4), one Ti(1), one Ti(2), and one Ti(3) atom to form distorted SCa2Ti3 trigonal bipyramids that share corners with two equivalent S(3)Ca2Ti3 trigonal bipyramids, corners with three equivalent S(6)Ca2Ti3 trigonal bipyramids, corners with four equivalent S(5)Ca2Ti3 trigonal bipyramids, edges with three equivalent S(1)Ca3Ti3 pentagonal pyramids,  an edgeedge with one S(3)Ca2Ti3 trigonal bipyramid,  an edgeedge with one S(5)Ca2Ti3 trigonal bipyramid,  an edgeedge with one S(6)Ca2Ti3 trigonal bipyramid, and  an edgeedge with one S(4)CaTi3 trigonal pyramid. In the sixth S site, S(6) is bonded to one Ca(2), one Ca(3), one Ti(1), one Ti(2), and one Ti(3) atom to form distorted SCa2Ti3 trigonal bipyramids that share corners with two equivalent S(6)Ca2Ti3 trigonal bipyramids, corners with three equivalent S(5)Ca2Ti3 trigonal bipyramids, corners with two equivalent S(4)CaTi3 trigonal pyramids,  an edgeedge with one S(1)Ca3Ti3 pentagonal pyramid,  an edgeedge with one S(3)Ca2Ti3 trigonal bipyramid,  an edgeedge with one S(5)Ca2Ti3 trigonal bipyramid, edges with three equivalent S(6)Ca2Ti3 trigonal bipyramids, and  an edgeedge with one S(4)CaTi3 trigonal pyramid.
Ca5(TiS2)8 crystallizes in the monoclinic C2/m space group. There are four inequivalent Ca sites. In the first Ca site, Ca(1) is bonded to two equivalent S(1) and four equivalent S(5) atoms to form distorted CaS6 octahedra that share corners with four equivalent Ti(2)S6 octahedra, corners with eight equivalent Ti(3)S6 octahedra, edges with four equivalent Ca(4)S6 octahedra, and faces with two equivalent Ti(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 44-48°. Both Ca(1)-S(1) bond lengths are 2.84 Å. All Ca(1)-S(5) bond lengths are 2.74 Å. In the second Ca site, Ca(2) is bonded to two equivalent S(2) and four equivalent S(6) atoms to form distorted CaS6 octahedra that share corners with four equivalent Ti(2)S6 octahedra, corners with eight equivalent Ti(3)S6 octahedra, edges with two equivalent Ca(3)S6 octahedra, and faces with two equivalent Ti(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 45-49°. Both Ca(2)-S(2) bond lengths are 2.77 Å. All Ca(2)-S(6) bond lengths are 2.82 Å. In the third Ca site, Ca(3) is bonded to two equivalent S(4) and four equivalent S(6) atoms to form distorted CaS6 octahedra that share corners with four equivalent Ti(1)S6 octahedra, corners with eight equivalent Ti(3)S6 octahedra, edges with two equivalent Ca(2)S6 octahedra, and faces with two equivalent Ti(2)S6 octahedra. The corner-sharing octahedral tilt angles range from 48-53°. Both Ca(3)-S(4) bond lengths are 2.86 Å. All Ca(3)-S(6) bond lengths are 2.82 Å. In the fourth Ca site, Ca(4) is bonded to two equivalent S(1), two equivalent S(3), and two equivalent S(5) atoms to form distorted CaS6 octahedra that share corners with four equivalent Ti(1)S6 octahedra, corners with four equivalent Ti(2)S6 octahedra, corners with four equivalent Ti(3)S6 octahedra, edges with two equivalent Ca(1)S6 octahedra, edges with two equivalent Ca(4)S6 octahedra, and faces with two equivalent Ti(3)S6 octahedra. The corner-sharing octahedral tilt angles range from 47-50°. Both Ca(4)-S(1) bond lengths are 2.79 Å. Both Ca(4)-S(3) bond lengths are 2.79 Å. Both Ca(4)-S(5) bond lengths are 2.78 Å. There are three inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to one S(1), one S(2), two equivalent S(5), and two equivalent S(6) atoms to form TiS6 octahedra that share corners with two equivalent Ca(3)S6 octahedra, corners with four equivalent Ca(4)S6 octahedra, edges with two equivalent Ti(2)S6 octahedra, edges with four equivalent Ti(3)S6 octahedra,  a faceface with one Ca(1)S6 octahedra, and  a faceface with one Ca(2)S6 octahedra. The corner-sharing octahedral tilt angles range from 48-49°. The Ti(1)-S(1) bond length is 2.63 Å. The Ti(1)-S(2) bond length is 2.43 Å. Both Ti(1)-S(5) bond lengths are 2.48 Å. Both Ti(1)-S(6) bond lengths are 2.54 Å. In the second Ti site, Ti(2) is bonded to one S(3), one S(4), two equivalent S(5), and two equivalent S(6) atoms to form TiS6 octahedra that share corners with two equivalent Ca(1)S6 octahedra, corners with two equivalent Ca(2)S6 octahedra, corners with four equivalent Ca(4)S6 octahedra, edges with two equivalent Ti(1)S6 octahedra, edges with four equivalent Ti(3)S6 octahedra, and  a faceface with one Ca(3)S6 octahedra. The corner-sharing octahedral tilt angles range from 44-50°. The Ti(2)-S(3) bond length is 2.54 Å. The Ti(2)-S(4) bond length is 2.43 Å. Both Ti(2)-S(5) bond lengths are 2.49 Å. Both Ti(2)-S(6) bond lengths are 2.51 Å. In the third Ti site, Ti(3) is bonded to one S(1), one S(2), one S(3), one S(4), one S(5), and one S(6) atom to form TiS6 octahedra that share corners with two equivalent Ca(1)S6 octahedra, corners with two equivalent Ca(2)S6 octahedra, corners with two equivalent Ca(3)S6 octahedra, corners with two equivalent Ca(4)S6 octahedra, edges with two equivalent Ti(1)S6 octahedra, edges with two equivalent Ti(2)S6 octahedra, edges with two equivalent Ti(3)S6 octahedra, and  a faceface with one Ca(4)S6 octahedra. The corner-sharing octahedral tilt angles range from 46-53°. The Ti(3)-S(1) bond length is 2.68 Å. The Ti(3)-S(2) bond length is 2.42 Å. The Ti(3)-S(3) bond length is 2.51 Å. The Ti(3)-S(4) bond length is 2.48 Å. The Ti(3)-S(5) bond length is 2.45 Å. The Ti(3)-S(6) bond length is 2.56 Å. There are six inequivalent S sites. In the first S site, S(1) is bonded to one Ca(1), two equivalent Ca(4), one Ti(1), and two equivalent Ti(3) atoms to form distorted SCa3Ti3 pentagonal pyramids that share corners with three equivalent S(1)Ca3Ti3 pentagonal pyramids, edges with two equivalent S(6)Ca2Ti3 trigonal bipyramids, edges with three equivalent S(3)Ca2Ti3 trigonal bipyramids, edges with six equivalent S(5)Ca2Ti3 trigonal bipyramids, and  an edgeedge with one S(4)CaTi3 trigonal pyramid. In the second S site, S(2) is bonded in a rectangular see-saw-like geometry to one Ca(2), one Ti(1), and two equivalent Ti(3) atoms. In the third S site, S(3) is bonded to two equivalent Ca(4), one Ti(2), and two equivalent Ti(3) atoms to form distorted SCa2Ti3 trigonal bipyramids that share corners with two equivalent S(3)Ca2Ti3 trigonal bipyramids, corners with four equivalent S(5)Ca2Ti3 trigonal bipyramids, corners with three equivalent S(4)CaTi3 trigonal pyramids, edges with three equivalent S(1)Ca3Ti3 pentagonal pyramids, edges with two equivalent S(5)Ca2Ti3 trigonal bipyramids, and edges with two equivalent S(6)Ca2Ti3 trigonal bipyramids. In the fourth S site, S(4) is bonded to one Ca(3), one Ti(2), and two equivalent Ti(3) atoms to form SCaTi3 trigonal pyramids that share corners with three equivalent S(3)Ca2Ti3 trigonal bipyramids, corners with four equivalent S(6)Ca2Ti3 trigonal bipyramids,  a cornercorner with one S(4)CaTi3 trigonal pyramid,  an edgeedge with one S(1)Ca3Ti3 pentagonal pyramid, edges with two equivalent S(5)Ca2Ti3 trigonal bipyramids, and edges with two equivalent S(6)Ca2Ti3 trigonal bipyramids. In the fifth S site, S(5) is bonded to one Ca(1), one Ca(4), one Ti(1), one Ti(2), and one Ti(3) atom to form distorted SCa2Ti3 trigonal bipyramids that share corners with two equivalent S(3)Ca2Ti3 trigonal bipyramids, corners with three equivalent S(6)Ca2Ti3 trigonal bipyramids, corners with four equivalent S(5)Ca2Ti3 trigonal bipyramids, edges with three equivalent S(1)Ca3Ti3 pentagonal pyramids,  an edgeedge with one S(3)Ca2Ti3 trigonal bipyramid,  an edgeedge with one S(5)Ca2Ti3 trigonal bipyramid,  an edgeedge with one S(6)Ca2Ti3 trigonal bipyramid, and  an edgeedge with one S(4)CaTi3 trigonal pyramid. In the sixth S site, S(6) is bonded to one Ca(2), one Ca(3), one Ti(1), one Ti(2), and one Ti(3) atom to form distorted SCa2Ti3 trigonal bipyramids that share corners with two equivalent S(6)Ca2Ti3 trigonal bipyramids, corners with three equivalent S(5)Ca2Ti3 trigonal bipyramids, corners with two equivalent S(4)CaTi3 trigonal pyramids,  an edgeedge with one S(1)Ca3Ti3 pentagonal pyramid,  an edgeedge with one S(3)Ca2Ti3 trigonal bipyramid,  an edgeedge with one S(5)Ca2Ti3 trigonal bipyramid, edges with three equivalent S(6)Ca2Ti3 trigonal bipyramids, and  an edgeedge with one S(4)CaTi3 trigonal pyramid.