Li20Si3P3S23Cl is Hausmannite-derived structured and crystallizes in the monoclinic Pm space group. There are twelve inequivalent Li sites. In the first Li site, Li(1) is bonded in a 4-coordinate geometry to one S(1), one S(10), one S(15), and one Cl(1) atom. In the second Li site, Li(2) is bonded in a 4-coordinate geometry to one S(1), one S(10), one S(14), and one S(17) atom. In the third Li site, Li(3) is bonded in a 4-coordinate geometry to one S(11), one S(13), one S(16), and one S(2) atom. In the fourth Li site, Li(4) is bonded in a 4-coordinate geometry to one S(12), one S(13), one S(16), and one S(3) atom. In the fifth Li site, Li(5) is bonded to one S(2), one S(3), two equivalent S(13), and two equivalent S(7) atoms to form LiS6 octahedra that share corners with two equivalent P(3)S4 tetrahedra,  an edgeedge with one Si(3)S4 tetrahedra,  an edgeedge with one P(1)S4 tetrahedra, edges with two equivalent Li(10)S4 tetrahedra, and edges with two equivalent Li(9)S4 tetrahedra. In the sixth Li site, Li(6) is bonded to one S(14), one S(15), one S(8), one S(9), and two equivalent S(1) atoms to form distorted LiS6 octahedra that share corners with two equivalent P(2)S4 tetrahedra,  an edgeedge with one Si(3)S4 tetrahedra, and  an edgeedge with one P(1)S4 tetrahedra. In the seventh Li site, Li(7) is bonded to one S(5), one S(6), two equivalent S(10), and two equivalent S(16) atoms to form distorted LiS6 octahedra that share corners with two equivalent P(2)S4 tetrahedra,  an edgeedge with one Si(2)S3Cl tetrahedra, and  an edgeedge with one Si(1)S4 tetrahedra. In the eighth Li site, Li(8) is bonded in a 6-coordinate geometry to one S(11), one S(12), one S(17), two equivalent S(4), and one Cl(1) atom. In the ninth Li site, Li(9) is bonded to one S(11), one S(2), one S(4), and one S(7) atom to form distorted LiS4 tetrahedra that share  a cornercorner with one Si(1)S4 tetrahedra,  a cornercorner with one P(1)S4 tetrahedra, corners with two equivalent Li(10)S4 tetrahedra, corners with two equivalent Li(9)S4 tetrahedra,  an edgeedge with one Li(5)S6 octahedra, and  an edgeedge with one P(3)S4 tetrahedra. In the tenth Li site, Li(10) is bonded to one S(12), one S(3), one S(4), and one S(7) atom to form distorted LiS4 tetrahedra that share  a cornercorner with one Si(1)S4 tetrahedra,  a cornercorner with one P(1)S4 tetrahedra, corners with two equivalent Li(10)S4 tetrahedra, corners with two equivalent Li(9)S4 tetrahedra,  an edgeedge with one Li(5)S6 octahedra, and  an edgeedge with one P(3)S4 tetrahedra. In the eleventh Li site, Li(11) is bonded in a 5-coordinate geometry to one S(1), one S(10), one S(16), one S(5), and one S(8) atom. In the twelfth Li site, Li(12) is bonded in a 5-coordinate geometry to one S(1), one S(10), one S(16), one S(6), and one S(9) atom. There are three inequivalent Si sites. In the first Si site, Si(1) is bonded to one S(11), one S(12), and two equivalent S(16) atoms to form SiS4 tetrahedra that share corners with two equivalent Li(10)S4 tetrahedra, corners with two equivalent Li(9)S4 tetrahedra, and  an edgeedge with one Li(7)S6 octahedra. In the second Si site, Si(2) is bonded to one S(17), two equivalent S(10), and one Cl(1) atom to form SiS3Cl tetrahedra that share  an edgeedge with one Li(7)S6 octahedra. In the third Si site, Si(3) is bonded to one S(8), one S(9), and two equivalent S(13) atoms to form SiS4 tetrahedra that share  an edgeedge with one Li(5)S6 octahedra and  an edgeedge with one Li(6)S6 octahedra. There are three inequivalent P sites. In the first P site, P(1) is bonded to one S(14), one S(15), and two equivalent S(7) atoms to form PS4 tetrahedra that share corners with two equivalent Li(10)S4 tetrahedra, corners with two equivalent Li(9)S4 tetrahedra,  an edgeedge with one Li(5)S6 octahedra, and  an edgeedge with one Li(6)S6 octahedra. In the second P site, P(2) is bonded to one S(5), one S(6), and two equivalent S(1) atoms to form PS4 tetrahedra that share corners with two equivalent Li(6)S6 octahedra and corners with two equivalent Li(7)S6 octahedra. The corner-sharing octahedral tilt angles range from 43-46°. In the third P site, P(3) is bonded to one S(2), one S(3), and two equivalent S(4) atoms to form PS4 tetrahedra that share corners with two equivalent Li(5)S6 octahedra, edges with two equivalent Li(10)S4 tetrahedra, and edges with two equivalent Li(9)S4 tetrahedra. The corner-sharing octahedral tilt angles range from 39-42°. There are seventeen inequivalent S sites. In the first S site, S(1) is bonded in a 6-coordinate geometry to one Li(1), one Li(11), one Li(12), one Li(2), one Li(6), and one P(2) atom. In the second S site, S(2) is bonded to one Li(5), two equivalent Li(3), two equivalent Li(9), and one P(3) atom to form distorted SLi5P octahedra that share corners with two equivalent S(3)Li5P octahedra, edges with two equivalent S(4)Li3P trigonal pyramids, and edges with two equivalent S(7)Li3P trigonal pyramids. The corner-sharing octahedral tilt angles range from 10-70°. In the third S site, S(3) is bonded to one Li(5), two equivalent Li(10), two equivalent Li(4), and one P(3) atom to form distorted SLi5P octahedra that share corners with two equivalent S(2)Li5P octahedra, edges with two equivalent S(4)Li3P trigonal pyramids, and edges with two equivalent S(7)Li3P trigonal pyramids. The corner-sharing octahedral tilt angles range from 10-70°. In the fourth S site, S(4) is bonded to one Li(10), one Li(8), one Li(9), and one P(3) atom to form distorted SLi3P trigonal pyramids that share  a cornercorner with one S(17)Li3Si trigonal pyramid,  a cornercorner with one Cl(1)Li3Si trigonal pyramid, corners with two equivalent S(4)Li3P trigonal pyramids, corners with two equivalent S(7)Li3P trigonal pyramids,  an edgeedge with one S(2)Li5P octahedra, and  an edgeedge with one S(3)Li5P octahedra. In the fifth S site, S(5) is bonded to one Li(7), two equivalent Li(11), and one P(2) atom to form distorted corner-sharing SLi3P trigonal pyramids. In the sixth S site, S(6) is bonded in a 4-coordinate geometry to one Li(7), two equivalent Li(12), and one P(2) atom. In the seventh S site, S(7) is bonded to one Li(10), one Li(5), one Li(9), and one P(1) atom to form distorted SLi3P trigonal pyramids that share corners with two equivalent S(4)Li3P trigonal pyramids,  an edgeedge with one S(2)Li5P octahedra,  an edgeedge with one S(3)Li5P octahedra, and  an edgeedge with one S(7)Li3P trigonal pyramid. In the eighth S site, S(8) is bonded to one Li(6), two equivalent Li(11), and one Si(3) atom to form SLi3Si trigonal pyramids that share corners with two equivalent S(5)Li3P trigonal pyramids and  an edgeedge with one S(9)Li3Si trigonal pyramid. In the ninth S site, S(9) is bonded to one Li(6), two equivalent Li(12), and one Si(3) atom to form edge-sharing SLi3Si trigonal pyramids. In the tenth S site, S(10) is bonded in a 6-coordinate geometry to one Li(1), one Li(11), one Li(12), one Li(2), one Li(7), and one Si(2) atom. In the eleventh S site, S(11) is bonded in a distorted hexagonal planar geometry to one Li(8), two equivalent Li(3), two equivalent Li(9), and one Si(1) atom. In the twelfth S site, S(12) is bonded in a distorted hexagonal planar geometry to one Li(8), two equivalent Li(10), two equivalent Li(4), and one Si(1) atom. In the thirteenth S site, S(13) is bonded in a rectangular see-saw-like geometry to one Li(3), one Li(4), one Li(5), and one Si(3) atom. In the fourteenth S site, S(14) is bonded in a rectangular see-saw-like geometry to one Li(6), two equivalent Li(2), and one P(1) atom. In the fifteenth S site, S(15) is bonded in a rectangular see-saw-like geometry to one Li(6), two equivalent Li(1), and one P(1) atom. In the sixteenth S site, S(16) is bonded in a 6-coordinate geometry to one Li(11), one Li(12), one Li(3), one Li(4), one Li(7), and one Si(1) atom. In the seventeenth S site, S(17) is bonded to one Li(8), two equivalent Li(2), and one Si(2) atom to form SLi3Si trigonal pyramids that share corners with two equivalent S(4)Li3P trigonal pyramids and  an edgeedge with one Cl(1)Li3Si trigonal pyramid. Cl(1) is bonded to one Li(8), two equivalent Li(1), and one Si(2) atom to form ClLi3Si trigonal pyramids that share corners with two equivalent S(4)Li3P trigonal pyramids and  an edgeedge with one S(17)Li3Si trigonal pyramid.
Li20Si3P3S23Cl is Hausmannite-derived structured and crystallizes in the monoclinic Pm space group. There are twelve inequivalent Li sites. In the first Li site, Li(1) is bonded in a 4-coordinate geometry to one S(1), one S(10), one S(15), and one Cl(1) atom. The Li(1)-S(1) bond length is 2.48 Å. The Li(1)-S(10) bond length is 2.65 Å. The Li(1)-S(15) bond length is 2.36 Å. The Li(1)-Cl(1) bond length is 2.40 Å. In the second Li site, Li(2) is bonded in a 4-coordinate geometry to one S(1), one S(10), one S(14), and one S(17) atom. The Li(2)-S(1) bond length is 2.51 Å. The Li(2)-S(10) bond length is 2.85 Å. The Li(2)-S(14) bond length is 2.40 Å. The Li(2)-S(17) bond length is 2.41 Å. In the third Li site, Li(3) is bonded in a 4-coordinate geometry to one S(11), one S(13), one S(16), and one S(2) atom. The Li(3)-S(11) bond length is 2.87 Å. The Li(3)-S(13) bond length is 2.36 Å. The Li(3)-S(16) bond length is 2.38 Å. The Li(3)-S(2) bond length is 2.61 Å. In the fourth Li site, Li(4) is bonded in a 4-coordinate geometry to one S(12), one S(13), one S(16), and one S(3) atom. The Li(4)-S(12) bond length is 2.80 Å. The Li(4)-S(13) bond length is 2.35 Å. The Li(4)-S(16) bond length is 2.38 Å. The Li(4)-S(3) bond length is 2.61 Å. In the fifth Li site, Li(5) is bonded to one S(2), one S(3), two equivalent S(13), and two equivalent S(7) atoms to form LiS6 octahedra that share corners with two equivalent P(3)S4 tetrahedra,  an edgeedge with one Si(3)S4 tetrahedra,  an edgeedge with one P(1)S4 tetrahedra, edges with two equivalent Li(10)S4 tetrahedra, and edges with two equivalent Li(9)S4 tetrahedra. The Li(5)-S(2) bond length is 2.72 Å. The Li(5)-S(3) bond length is 2.69 Å. Both Li(5)-S(13) bond lengths are 2.52 Å. Both Li(5)-S(7) bond lengths are 2.72 Å. In the sixth Li site, Li(6) is bonded to one S(14), one S(15), one S(8), one S(9), and two equivalent S(1) atoms to form distorted LiS6 octahedra that share corners with two equivalent P(2)S4 tetrahedra,  an edgeedge with one Si(3)S4 tetrahedra, and  an edgeedge with one P(1)S4 tetrahedra. The Li(6)-S(14) bond length is 2.79 Å. The Li(6)-S(15) bond length is 2.80 Å. The Li(6)-S(8) bond length is 2.57 Å. The Li(6)-S(9) bond length is 2.54 Å. Both Li(6)-S(1) bond lengths are 2.74 Å. In the seventh Li site, Li(7) is bonded to one S(5), one S(6), two equivalent S(10), and two equivalent S(16) atoms to form distorted LiS6 octahedra that share corners with two equivalent P(2)S4 tetrahedra,  an edgeedge with one Si(2)S3Cl tetrahedra, and  an edgeedge with one Si(1)S4 tetrahedra. The Li(7)-S(5) bond length is 2.73 Å. The Li(7)-S(6) bond length is 2.78 Å. Both Li(7)-S(10) bond lengths are 2.67 Å. Both Li(7)-S(16) bond lengths are 2.55 Å. In the eighth Li site, Li(8) is bonded in a 6-coordinate geometry to one S(11), one S(12), one S(17), two equivalent S(4), and one Cl(1) atom. The Li(8)-S(11) bond length is 2.49 Å. The Li(8)-S(12) bond length is 2.45 Å. The Li(8)-S(17) bond length is 2.66 Å. Both Li(8)-S(4) bond lengths are 2.80 Å. The Li(8)-Cl(1) bond length is 2.92 Å. In the ninth Li site, Li(9) is bonded to one S(11), one S(2), one S(4), and one S(7) atom to form distorted LiS4 tetrahedra that share  a cornercorner with one Si(1)S4 tetrahedra,  a cornercorner with one P(1)S4 tetrahedra, corners with two equivalent Li(10)S4 tetrahedra, corners with two equivalent Li(9)S4 tetrahedra,  an edgeedge with one Li(5)S6 octahedra, and  an edgeedge with one P(3)S4 tetrahedra. The Li(9)-S(11) bond length is 2.65 Å. The Li(9)-S(2) bond length is 2.55 Å. The Li(9)-S(4) bond length is 2.46 Å. The Li(9)-S(7) bond length is 2.50 Å. In the tenth Li site, Li(10) is bonded to one S(12), one S(3), one S(4), and one S(7) atom to form distorted LiS4 tetrahedra that share  a cornercorner with one Si(1)S4 tetrahedra,  a cornercorner with one P(1)S4 tetrahedra, corners with two equivalent Li(10)S4 tetrahedra, corners with two equivalent Li(9)S4 tetrahedra,  an edgeedge with one Li(5)S6 octahedra, and  an edgeedge with one P(3)S4 tetrahedra. The Li(10)-S(12) bond length is 2.68 Å. The Li(10)-S(3) bond length is 2.62 Å. The Li(10)-S(4) bond length is 2.45 Å. The Li(10)-S(7) bond length is 2.50 Å. In the eleventh Li site, Li(11) is bonded in a 5-coordinate geometry to one S(1), one S(10), one S(16), one S(5), and one S(8) atom. The Li(11)-S(1) bond length is 2.93 Å. The Li(11)-S(10) bond length is 2.69 Å. The Li(11)-S(16) bond length is 2.93 Å. The Li(11)-S(5) bond length is 2.39 Å. The Li(11)-S(8) bond length is 2.39 Å. In the twelfth Li site, Li(12) is bonded in a 5-coordinate geometry to one S(1), one S(10), one S(16), one S(6), and one S(9) atom. The Li(12)-S(1) bond length is 3.01 Å. The Li(12)-S(10) bond length is 2.71 Å. The Li(12)-S(16) bond length is 2.92 Å. The Li(12)-S(6) bond length is 2.39 Å. The Li(12)-S(9) bond length is 2.38 Å. There are three inequivalent Si sites. In the first Si site, Si(1) is bonded to one S(11), one S(12), and two equivalent S(16) atoms to form SiS4 tetrahedra that share corners with two equivalent Li(10)S4 tetrahedra, corners with two equivalent Li(9)S4 tetrahedra, and  an edgeedge with one Li(7)S6 octahedra. The Si(1)-S(11) bond length is 2.16 Å. The Si(1)-S(12) bond length is 2.16 Å. Both Si(1)-S(16) bond lengths are 2.15 Å. In the second Si site, Si(2) is bonded to one S(17), two equivalent S(10), and one Cl(1) atom to form SiS3Cl tetrahedra that share  an edgeedge with one Li(7)S6 octahedra. The Si(2)-S(17) bond length is 2.09 Å. Both Si(2)-S(10) bond lengths are 2.11 Å. The Si(2)-Cl(1) bond length is 2.26 Å. In the third Si site, Si(3) is bonded to one S(8), one S(9), and two equivalent S(13) atoms to form SiS4 tetrahedra that share  an edgeedge with one Li(5)S6 octahedra and  an edgeedge with one Li(6)S6 octahedra. The Si(3)-S(8) bond length is 2.16 Å. The Si(3)-S(9) bond length is 2.15 Å. Both Si(3)-S(13) bond lengths are 2.13 Å. There are three inequivalent P sites. In the first P site, P(1) is bonded to one S(14), one S(15), and two equivalent S(7) atoms to form PS4 tetrahedra that share corners with two equivalent Li(10)S4 tetrahedra, corners with two equivalent Li(9)S4 tetrahedra,  an edgeedge with one Li(5)S6 octahedra, and  an edgeedge with one Li(6)S6 octahedra. The P(1)-S(14) bond length is 2.05 Å. The P(1)-S(15) bond length is 2.05 Å. Both P(1)-S(7) bond lengths are 2.07 Å. In the second P site, P(2) is bonded to one S(5), one S(6), and two equivalent S(1) atoms to form PS4 tetrahedra that share corners with two equivalent Li(6)S6 octahedra and corners with two equivalent Li(7)S6 octahedra. The corner-sharing octahedral tilt angles range from 43-46°. The P(2)-S(5) bond length is 2.05 Å. The P(2)-S(6) bond length is 2.04 Å. Both P(2)-S(1) bond lengths are 2.07 Å. In the third P site, P(3) is bonded to one S(2), one S(3), and two equivalent S(4) atoms to form PS4 tetrahedra that share corners with two equivalent Li(5)S6 octahedra, edges with two equivalent Li(10)S4 tetrahedra, and edges with two equivalent Li(9)S4 tetrahedra. The corner-sharing octahedral tilt angles range from 39-42°. The P(3)-S(2) bond length is 2.07 Å. The P(3)-S(3) bond length is 2.07 Å. Both P(3)-S(4) bond lengths are 2.05 Å. There are seventeen inequivalent S sites. In the first S site, S(1) is bonded in a 6-coordinate geometry to one Li(1), one Li(11), one Li(12), one Li(2), one Li(6), and one P(2) atom. In the second S site, S(2) is bonded to one Li(5), two equivalent Li(3), two equivalent Li(9), and one P(3) atom to form distorted SLi5P octahedra that share corners with two equivalent S(3)Li5P octahedra, edges with two equivalent S(4)Li3P trigonal pyramids, and edges with two equivalent S(7)Li3P trigonal pyramids. The corner-sharing octahedral tilt angles range from 10-70°. In the third S site, S(3) is bonded to one Li(5), two equivalent Li(10), two equivalent Li(4), and one P(3) atom to form distorted SLi5P octahedra that share corners with two equivalent S(2)Li5P octahedra, edges with two equivalent S(4)Li3P trigonal pyramids, and edges with two equivalent S(7)Li3P trigonal pyramids. The corner-sharing octahedral tilt angles range from 10-70°. In the fourth S site, S(4) is bonded to one Li(10), one Li(8), one Li(9), and one P(3) atom to form distorted SLi3P trigonal pyramids that share  a cornercorner with one S(17)Li3Si trigonal pyramid,  a cornercorner with one Cl(1)Li3Si trigonal pyramid, corners with two equivalent S(4)Li3P trigonal pyramids, corners with two equivalent S(7)Li3P trigonal pyramids,  an edgeedge with one S(2)Li5P octahedra, and  an edgeedge with one S(3)Li5P octahedra. In the fifth S site, S(5) is bonded to one Li(7), two equivalent Li(11), and one P(2) atom to form distorted corner-sharing SLi3P trigonal pyramids. In the sixth S site, S(6) is bonded in a 4-coordinate geometry to one Li(7), two equivalent Li(12), and one P(2) atom. In the seventh S site, S(7) is bonded to one Li(10), one Li(5), one Li(9), and one P(1) atom to form distorted SLi3P trigonal pyramids that share corners with two equivalent S(4)Li3P trigonal pyramids,  an edgeedge with one S(2)Li5P octahedra,  an edgeedge with one S(3)Li5P octahedra, and  an edgeedge with one S(7)Li3P trigonal pyramid. In the eighth S site, S(8) is bonded to one Li(6), two equivalent Li(11), and one Si(3) atom to form SLi3Si trigonal pyramids that share corners with two equivalent S(5)Li3P trigonal pyramids and  an edgeedge with one S(9)Li3Si trigonal pyramid. In the ninth S site, S(9) is bonded to one Li(6), two equivalent Li(12), and one Si(3) atom to form edge-sharing SLi3Si trigonal pyramids. In the tenth S site, S(10) is bonded in a 6-coordinate geometry to one Li(1), one Li(11), one Li(12), one Li(2), one Li(7), and one Si(2) atom. In the eleventh S site, S(11) is bonded in a distorted hexagonal planar geometry to one Li(8), two equivalent Li(3), two equivalent Li(9), and one Si(1) atom. In the twelfth S site, S(12) is bonded in a distorted hexagonal planar geometry to one Li(8), two equivalent Li(10), two equivalent Li(4), and one Si(1) atom. In the thirteenth S site, S(13) is bonded in a rectangular see-saw-like geometry to one Li(3), one Li(4), one Li(5), and one Si(3) atom. In the fourteenth S site, S(14) is bonded in a rectangular see-saw-like geometry to one Li(6), two equivalent Li(2), and one P(1) atom. In the fifteenth S site, S(15) is bonded in a rectangular see-saw-like geometry to one Li(6), two equivalent Li(1), and one P(1) atom. In the sixteenth S site, S(16) is bonded in a 6-coordinate geometry to one Li(11), one Li(12), one Li(3), one Li(4), one Li(7), and one Si(1) atom. In the seventeenth S site, S(17) is bonded to one Li(8), two equivalent Li(2), and one Si(2) atom to form SLi3Si trigonal pyramids that share corners with two equivalent S(4)Li3P trigonal pyramids and  an edgeedge with one Cl(1)Li3Si trigonal pyramid. Cl(1) is bonded to one Li(8), two equivalent Li(1), and one Si(2) atom to form ClLi3Si trigonal pyramids that share corners with two equivalent S(4)Li3P trigonal pyramids and  an edgeedge with one S(17)Li3Si trigonal pyramid.