Hf8Mo5S crystallizes in the orthorhombic Amm2 space group. There are seven inequivalent Hf sites. In the first Hf site, Hf(1) is bonded in a 1-coordinate geometry to one Mo(1), one Mo(2), one Mo(3), one Mo(4), one Mo(6), and one S(1) atom. In the second Hf site, Hf(2) is bonded in a 1-coordinate geometry to one Mo(1), one Mo(5), two equivalent Mo(2), two equivalent Mo(6), and one S(1) atom. In the third Hf site, Hf(3) is bonded in a 1-coordinate geometry to one Mo(1), one Mo(2), one Mo(4), one Mo(5), one Mo(6), and one S(2) atom. In the fourth Hf site, Hf(4) is bonded in a 7-coordinate geometry to one Mo(1), one Mo(3), two equivalent Mo(4), two equivalent Mo(6), and one S(2) atom. In the fifth Hf site, Hf(5) is bonded in a 5-coordinate geometry to two equivalent Mo(2), two equivalent Mo(6), and one S(1) atom. In the sixth Hf site, Hf(6) is bonded in a linear geometry to one Mo(4) and one Mo(5) atom. In the seventh Hf site, Hf(7) is bonded in a 1-coordinate geometry to two equivalent Mo(4) and one S(2) atom. There are six inequivalent Mo sites. In the first Mo site, Mo(1) is bonded to one Hf(2), one Hf(4), two equivalent Hf(1), two equivalent Hf(3), one Mo(3), one Mo(5), two equivalent Mo(2), and two equivalent Mo(4) atoms to form face-sharing MoHf6Mo6 cuboctahedra. In the second Mo site, Mo(2) is bonded in a 12-coordinate geometry to one Hf(5), two equivalent Hf(1), two equivalent Hf(2), two equivalent Hf(3), one Mo(2), one Mo(3), one Mo(6), and two equivalent Mo(1) atoms. In the third Mo site, Mo(3) is bonded in a 12-coordinate geometry to two equivalent Hf(4), four equivalent Hf(1), two equivalent Mo(1), two equivalent Mo(2), and two equivalent Mo(6) atoms. In the fourth Mo site, Mo(4) is bonded in a 12-coordinate geometry to one Hf(6), one Hf(7), two equivalent Hf(1), two equivalent Hf(3), two equivalent Hf(4), one Mo(4), one Mo(5), and two equivalent Mo(1) atoms. In the fifth Mo site, Mo(5) is bonded in a 12-coordinate geometry to two equivalent Hf(2), two equivalent Hf(6), four equivalent Hf(3), two equivalent Mo(1), and two equivalent Mo(4) atoms. In the sixth Mo site, Mo(6) is bonded in a 12-coordinate geometry to one Hf(5), two equivalent Hf(1), two equivalent Hf(2), two equivalent Hf(3), two equivalent Hf(4), one Mo(2), one Mo(3), and one Mo(6) atom. There are two inequivalent S sites. In the first S site, S(1) is bonded in a 7-coordinate geometry to one Hf(5), two equivalent Hf(2), and four equivalent Hf(1) atoms. In the second S site, S(2) is bonded in a 7-coordinate geometry to one Hf(7), two equivalent Hf(4), and four equivalent Hf(3) atoms.
Hf8Mo5S crystallizes in the orthorhombic Amm2 space group. There are seven inequivalent Hf sites. In the first Hf site, Hf(1) is bonded in a 1-coordinate geometry to one Mo(1), one Mo(2), one Mo(3), one Mo(4), one Mo(6), and one S(1) atom. The Hf(1)-Mo(1) bond length is 3.04 Å. The Hf(1)-Mo(2) bond length is 3.03 Å. The Hf(1)-Mo(3) bond length is 3.08 Å. The Hf(1)-Mo(4) bond length is 2.93 Å. The Hf(1)-Mo(6) bond length is 3.10 Å. The Hf(1)-S(1) bond length is 2.57 Å. In the second Hf site, Hf(2) is bonded in a 1-coordinate geometry to one Mo(1), one Mo(5), two equivalent Mo(2), two equivalent Mo(6), and one S(1) atom. The Hf(2)-Mo(1) bond length is 2.95 Å. The Hf(2)-Mo(5) bond length is 2.94 Å. Both Hf(2)-Mo(2) bond lengths are 3.01 Å. Both Hf(2)-Mo(6) bond lengths are 3.39 Å. The Hf(2)-S(1) bond length is 2.73 Å. In the third Hf site, Hf(3) is bonded in a 1-coordinate geometry to one Mo(1), one Mo(2), one Mo(4), one Mo(5), one Mo(6), and one S(2) atom. The Hf(3)-Mo(1) bond length is 3.06 Å. The Hf(3)-Mo(2) bond length is 2.85 Å. The Hf(3)-Mo(4) bond length is 3.09 Å. The Hf(3)-Mo(5) bond length is 3.15 Å. The Hf(3)-Mo(6) bond length is 3.05 Å. The Hf(3)-S(2) bond length is 2.65 Å. In the fourth Hf site, Hf(4) is bonded in a 7-coordinate geometry to one Mo(1), one Mo(3), two equivalent Mo(4), two equivalent Mo(6), and one S(2) atom. The Hf(4)-Mo(1) bond length is 2.96 Å. The Hf(4)-Mo(3) bond length is 2.83 Å. Both Hf(4)-Mo(4) bond lengths are 3.10 Å. Both Hf(4)-Mo(6) bond lengths are 3.15 Å. The Hf(4)-S(2) bond length is 2.67 Å. In the fifth Hf site, Hf(5) is bonded in a 5-coordinate geometry to two equivalent Mo(2), two equivalent Mo(6), and one S(1) atom. Both Hf(5)-Mo(2) bond lengths are 3.09 Å. Both Hf(5)-Mo(6) bond lengths are 2.78 Å. The Hf(5)-S(1) bond length is 2.87 Å. In the sixth Hf site, Hf(6) is bonded in a linear geometry to one Mo(4) and one Mo(5) atom. The Hf(6)-Mo(4) bond length is 2.77 Å. The Hf(6)-Mo(5) bond length is 2.83 Å. In the seventh Hf site, Hf(7) is bonded in a 1-coordinate geometry to two equivalent Mo(4) and one S(2) atom. Both Hf(7)-Mo(4) bond lengths are 3.07 Å. The Hf(7)-S(2) bond length is 2.67 Å. There are six inequivalent Mo sites. In the first Mo site, Mo(1) is bonded to one Hf(2), one Hf(4), two equivalent Hf(1), two equivalent Hf(3), one Mo(3), one Mo(5), two equivalent Mo(2), and two equivalent Mo(4) atoms to form face-sharing MoHf6Mo6 cuboctahedra. The Mo(1)-Mo(3) bond length is 2.69 Å. The Mo(1)-Mo(5) bond length is 2.66 Å. Both Mo(1)-Mo(2) bond lengths are 2.70 Å. Both Mo(1)-Mo(4) bond lengths are 2.72 Å. In the second Mo site, Mo(2) is bonded in a 12-coordinate geometry to one Hf(5), two equivalent Hf(1), two equivalent Hf(2), two equivalent Hf(3), one Mo(2), one Mo(3), one Mo(6), and two equivalent Mo(1) atoms. The Mo(2)-Mo(2) bond length is 2.94 Å. The Mo(2)-Mo(3) bond length is 2.92 Å. The Mo(2)-Mo(6) bond length is 2.80 Å. In the third Mo site, Mo(3) is bonded in a 12-coordinate geometry to two equivalent Hf(4), four equivalent Hf(1), two equivalent Mo(1), two equivalent Mo(2), and two equivalent Mo(6) atoms. Both Mo(3)-Mo(6) bond lengths are 2.71 Å. In the fourth Mo site, Mo(4) is bonded in a 12-coordinate geometry to one Hf(6), one Hf(7), two equivalent Hf(1), two equivalent Hf(3), two equivalent Hf(4), one Mo(4), one Mo(5), and two equivalent Mo(1) atoms. The Mo(4)-Mo(4) bond length is 2.99 Å. The Mo(4)-Mo(5) bond length is 2.82 Å. In the fifth Mo site, Mo(5) is bonded in a 12-coordinate geometry to two equivalent Hf(2), two equivalent Hf(6), four equivalent Hf(3), two equivalent Mo(1), and two equivalent Mo(4) atoms. In the sixth Mo site, Mo(6) is bonded in a 12-coordinate geometry to one Hf(5), two equivalent Hf(1), two equivalent Hf(2), two equivalent Hf(3), two equivalent Hf(4), one Mo(2), one Mo(3), and one Mo(6) atom. The Mo(6)-Mo(6) bond length is 3.16 Å. There are two inequivalent S sites. In the first S site, S(1) is bonded in a 7-coordinate geometry to one Hf(5), two equivalent Hf(2), and four equivalent Hf(1) atoms. In the second S site, S(2) is bonded in a 7-coordinate geometry to one Hf(7), two equivalent Hf(4), and four equivalent Hf(3) atoms.