MgTi2(PS3)4 crystallizes in the triclinic P1 space group. Mg(1) is bonded to one S(1), one S(2), one S(3), one S(4), and one S(9) atom to form distorted MgS5 square pyramids that share  a cornercorner with one Ti(1)S6 octahedra, corners with two equivalent P(2)S3 tetrahedra, and edges with two equivalent Ti(1)S6 octahedra. The corner-sharing octahedral tilt angles are 15°. There are two inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to one S(1), one S(10), one S(2), one S(3), one S(4), and one S(9) atom to form distorted TiS6 octahedra that share  a cornercorner with one Mg(1)S5 square pyramid, edges with two equivalent Mg(1)S5 square pyramids, and  an edgeedge with one P(2)S3 tetrahedra. In the second Ti site, Ti(2) is bonded to one S(11), one S(12), one S(5), one S(6), one S(7), and one S(8) atom to form TiS6 octahedra that share  a cornercorner with one P(2)S3 tetrahedra. There are four inequivalent P sites. In the first P site, P(1) is bonded in a distorted trigonal non-coplanar geometry to one S(11), one S(3), and one S(8) atom. In the second P site, P(2) is bonded to one S(1), one S(6), and one S(9) atom to form distorted PS3 tetrahedra that share  a cornercorner with one Ti(2)S6 octahedra, corners with two equivalent Mg(1)S5 square pyramids, and  an edgeedge with one Ti(1)S6 octahedra. The corner-sharing octahedral tilt angles are 75°. In the third P site, P(3) is bonded in a 3-coordinate geometry to one S(10), one S(2), and one S(5) atom. In the fourth P site, P(4) is bonded in a distorted trigonal non-coplanar geometry to one S(12), one S(4), and one S(7) atom. There are twelve inequivalent S sites. In the first S site, S(1) is bonded in a distorted T-shaped geometry to one Mg(1), one Ti(1), and one P(2) atom. In the second S site, S(2) is bonded in a distorted trigonal non-coplanar geometry to one Mg(1), one Ti(1), and one P(3) atom. In the third S site, S(3) is bonded in a distorted T-shaped geometry to one Mg(1), one Ti(1), and one P(1) atom. In the fourth S site, S(4) is bonded in a distorted trigonal non-coplanar geometry to one Mg(1), one Ti(1), and one P(4) atom. In the fifth S site, S(5) is bonded in a water-like geometry to one Ti(2) and one P(3) atom. In the sixth S site, S(6) is bonded in a water-like geometry to one Ti(2) and one P(2) atom. In the seventh S site, S(7) is bonded in an L-shaped geometry to one Ti(2) and one P(4) atom. In the eighth S site, S(8) is bonded in an L-shaped geometry to one Ti(2) and one P(1) atom. In the ninth S site, S(9) is bonded in a distorted T-shaped geometry to one Mg(1), one Ti(1), and one P(2) atom. In the tenth S site, S(10) is bonded in a distorted L-shaped geometry to one Ti(1) and one P(3) atom. In the eleventh S site, S(11) is bonded in an L-shaped geometry to one Ti(2) and one P(1) atom. In the twelfth S site, S(12) is bonded in an L-shaped geometry to one Ti(2) and one P(4) atom.
MgTi2(PS3)4 crystallizes in the triclinic P1 space group. Mg(1) is bonded to one S(1), one S(2), one S(3), one S(4), and one S(9) atom to form distorted MgS5 square pyramids that share  a cornercorner with one Ti(1)S6 octahedra, corners with two equivalent P(2)S3 tetrahedra, and edges with two equivalent Ti(1)S6 octahedra. The corner-sharing octahedral tilt angles are 15°. The Mg(1)-S(1) bond length is 2.65 Å. The Mg(1)-S(2) bond length is 2.62 Å. The Mg(1)-S(3) bond length is 2.70 Å. The Mg(1)-S(4) bond length is 2.69 Å. The Mg(1)-S(9) bond length is 2.75 Å. There are two inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to one S(1), one S(10), one S(2), one S(3), one S(4), and one S(9) atom to form distorted TiS6 octahedra that share  a cornercorner with one Mg(1)S5 square pyramid, edges with two equivalent Mg(1)S5 square pyramids, and  an edgeedge with one P(2)S3 tetrahedra. The Ti(1)-S(1) bond length is 2.59 Å. The Ti(1)-S(10) bond length is 2.51 Å. The Ti(1)-S(2) bond length is 2.60 Å. The Ti(1)-S(3) bond length is 2.39 Å. The Ti(1)-S(4) bond length is 2.39 Å. The Ti(1)-S(9) bond length is 2.57 Å. In the second Ti site, Ti(2) is bonded to one S(11), one S(12), one S(5), one S(6), one S(7), and one S(8) atom to form TiS6 octahedra that share  a cornercorner with one P(2)S3 tetrahedra. The Ti(2)-S(11) bond length is 2.54 Å. The Ti(2)-S(12) bond length is 2.54 Å. The Ti(2)-S(5) bond length is 2.46 Å. The Ti(2)-S(6) bond length is 2.47 Å. The Ti(2)-S(7) bond length is 2.48 Å. The Ti(2)-S(8) bond length is 2.48 Å. There are four inequivalent P sites. In the first P site, P(1) is bonded in a distorted trigonal non-coplanar geometry to one S(11), one S(3), and one S(8) atom. The P(1)-S(11) bond length is 2.00 Å. The P(1)-S(3) bond length is 2.11 Å. The P(1)-S(8) bond length is 2.01 Å. In the second P site, P(2) is bonded to one S(1), one S(6), and one S(9) atom to form distorted PS3 tetrahedra that share  a cornercorner with one Ti(2)S6 octahedra, corners with two equivalent Mg(1)S5 square pyramids, and  an edgeedge with one Ti(1)S6 octahedra. The corner-sharing octahedral tilt angles are 75°. The P(2)-S(1) bond length is 2.07 Å. The P(2)-S(6) bond length is 2.02 Å. The P(2)-S(9) bond length is 2.05 Å. In the third P site, P(3) is bonded in a 3-coordinate geometry to one S(10), one S(2), and one S(5) atom. The P(3)-S(10) bond length is 2.04 Å. The P(3)-S(2) bond length is 2.08 Å. The P(3)-S(5) bond length is 2.02 Å. In the fourth P site, P(4) is bonded in a distorted trigonal non-coplanar geometry to one S(12), one S(4), and one S(7) atom. The P(4)-S(12) bond length is 2.00 Å. The P(4)-S(4) bond length is 2.11 Å. The P(4)-S(7) bond length is 2.01 Å. There are twelve inequivalent S sites. In the first S site, S(1) is bonded in a distorted T-shaped geometry to one Mg(1), one Ti(1), and one P(2) atom. In the second S site, S(2) is bonded in a distorted trigonal non-coplanar geometry to one Mg(1), one Ti(1), and one P(3) atom. In the third S site, S(3) is bonded in a distorted T-shaped geometry to one Mg(1), one Ti(1), and one P(1) atom. In the fourth S site, S(4) is bonded in a distorted trigonal non-coplanar geometry to one Mg(1), one Ti(1), and one P(4) atom. In the fifth S site, S(5) is bonded in a water-like geometry to one Ti(2) and one P(3) atom. In the sixth S site, S(6) is bonded in a water-like geometry to one Ti(2) and one P(2) atom. In the seventh S site, S(7) is bonded in an L-shaped geometry to one Ti(2) and one P(4) atom. In the eighth S site, S(8) is bonded in an L-shaped geometry to one Ti(2) and one P(1) atom. In the ninth S site, S(9) is bonded in a distorted T-shaped geometry to one Mg(1), one Ti(1), and one P(2) atom. In the tenth S site, S(10) is bonded in a distorted L-shaped geometry to one Ti(1) and one P(3) atom. In the eleventh S site, S(11) is bonded in an L-shaped geometry to one Ti(2) and one P(1) atom. In the twelfth S site, S(12) is bonded in an L-shaped geometry to one Ti(2) and one P(4) atom.