Cd8C94S17 crystallizes in the hexagonal P6_222 space group. There are two inequivalent Cd sites. In the first Cd site, Cd(1) is bonded in a 5-coordinate geometry to one S(1), one S(2), one S(3), and two equivalent S(4) atoms. The Cd(1)-S(1) bond length is 2.56 Å. The Cd(1)-S(2) bond length is 2.55 Å. The Cd(1)-S(3) bond length is 2.54 Å. There is one shorter (2.50 Å) and one longer (2.65 Å) Cd(1)-S(4) bond length. In the second Cd site, Cd(2) is bonded to one S(1), one S(2), one S(3), and one S(5) atom to form corner-sharing CdS4 tetrahedra. The Cd(2)-S(1) bond length is 2.52 Å. The Cd(2)-S(2) bond length is 2.53 Å. The Cd(2)-S(3) bond length is 2.53 Å. The Cd(2)-S(5) bond length is 2.53 Å. There are twenty-four inequivalent C sites. In the first C site, C(1) is bonded in a trigonal planar geometry to one C(2), one C(6), and one S(1) atom. The C(1)-C(2) bond length is 1.39 Å. The C(1)-C(6) bond length is 1.39 Å. The C(1)-S(1) bond length is 1.73 Å. In the second C site, C(2) is bonded in a bent 120 degrees geometry to one C(1) and one C(3) atom. The C(2)-C(3) bond length is 1.39 Å. In the third C site, C(3) is bonded in a bent 120 degrees geometry to one C(2) and one C(4) atom. The C(3)-C(4) bond length is 1.39 Å. In the fourth C site, C(4) is bonded in a bent 120 degrees geometry to one C(3) and one C(5) atom. The C(4)-C(5) bond length is 1.39 Å. In the fifth C site, C(5) is bonded in a bent 120 degrees geometry to one C(4) and one C(6) atom. The C(5)-C(6) bond length is 1.39 Å. In the sixth C site, C(6) is bonded in a bent 120 degrees geometry to one C(1) and one C(5) atom. In the seventh C site, C(7) is bonded in a bent 120 degrees geometry to one C(24) and one C(8) atom. The C(7)-C(24) bond length is 1.38 Å. The C(7)-C(8) bond length is 1.22 Å. In the eighth C site, C(8) is bonded in a bent 120 degrees geometry to one C(7) and one C(9) atom. The C(8)-C(9) bond length is 1.19 Å. In the ninth C site, C(9) is bonded in a bent 150 degrees geometry to one C(8) and one C(9) atom. The C(9)-C(9) bond length is 1.10 Å. In the tenth C site, C(10) is bonded in a trigonal planar geometry to one C(11), one C(15), and one S(2) atom. The C(10)-C(11) bond length is 1.39 Å. The C(10)-C(15) bond length is 1.39 Å. The C(10)-S(2) bond length is 1.77 Å. In the eleventh C site, C(11) is bonded in a bent 120 degrees geometry to one C(10) and one C(12) atom. The C(11)-C(12) bond length is 1.39 Å. In the twelfth C site, C(12) is bonded in a trigonal planar geometry to one C(11), one C(13), and one C(16) atom. The C(12)-C(13) bond length is 1.39 Å. The C(12)-C(16) bond length is 1.29 Å. In the thirteenth C site, C(13) is bonded in a bent 120 degrees geometry to one C(12) and one C(14) atom. The C(13)-C(14) bond length is 1.39 Å. In the fourteenth C site, C(14) is bonded in a bent 120 degrees geometry to one C(13) and one C(15) atom. The C(14)-C(15) bond length is 1.39 Å. In the fifteenth C site, C(15) is bonded in a bent 120 degrees geometry to one C(10) and one C(14) atom. In the sixteenth C site, C(16) is bonded in a single-bond geometry to one C(12) atom. In the seventeenth C site, C(17) is bonded in a trigonal planar geometry to one C(18), one C(22), and one S(3) atom. The C(17)-C(18) bond length is 1.39 Å. The C(17)-C(22) bond length is 1.39 Å. The C(17)-S(3) bond length is 1.80 Å. In the eighteenth C site, C(18) is bonded in a bent 120 degrees geometry to one C(17) and one C(19) atom. The C(18)-C(19) bond length is 1.39 Å. In the nineteenth C site, C(19) is bonded in a trigonal planar geometry to one C(18), one C(20), and one C(23) atom. The C(19)-C(20) bond length is 1.39 Å. The C(19)-C(23) bond length is 1.59 Å. In the twentieth C site, C(20) is bonded in a bent 120 degrees geometry to one C(19) and one C(21) atom. The C(20)-C(21) bond length is 1.39 Å. In the twenty-first C site, C(21) is bonded in a bent 120 degrees geometry to one C(20) and one C(22) atom. The C(21)-C(22) bond length is 1.39 Å. In the twenty-second C site, C(22) is bonded in a bent 120 degrees geometry to one C(17) and one C(21) atom. In the twenty-third C site, C(23) is bonded in a single-bond geometry to one C(19) atom. In the twenty-fourth C site, C(24) is bonded in a 4-coordinate geometry to two equivalent C(7) and two equivalent S(4) atoms. Both C(24)-S(4) bond lengths are 1.80 Å. There are five inequivalent S sites. In the first S site, S(1) is bonded in a trigonal non-coplanar geometry to one Cd(1), one Cd(2), and one C(1) atom. In the second S site, S(2) is bonded in a trigonal non-coplanar geometry to one Cd(1), one Cd(2), and one C(10) atom. In the third S site, S(3) is bonded in a trigonal non-coplanar geometry to one Cd(1), one Cd(2), and one C(17) atom. In the fourth S site, S(4) is bonded in a 4-coordinate geometry to two equivalent Cd(1), one C(24), and one S(4) atom. The S(4)-S(4) bond length is 1.23 Å. In the fifth S site, S(5) is bonded in a tetrahedral geometry to four equivalent Cd(2) atoms. Linkers: 1 [S]S[C]1[C]=[C][C]=[C][C]=[C]1 ,2 [S]SC1=[C][C][C]=[C][C]=[C]1 ,1 [S]SC1=[C][C]=[C][C][C]=[C]1 ,2 [S]SC1=[C][C]=[C][C]=[C][C]1. Metal clusters: 24 [Cd]. The MOF has largest included sphere 4.68 A, density 1.66 g/cm3, surface area 4039.09 m2/g, accessible volume 0.21 cm3/g