MgTi2(PS3)4 crystallizes in the triclinic P1 space group. Mg(1) is bonded to one S(11), one S(3), one S(4), one S(7), and one S(8) atom to form distorted MgS5 trigonal bipyramids that share  a cornercorner with one Ti(2)S6 octahedra, corners with two equivalent Ti(1)S6 octahedra,  a cornercorner with one P(1)S3 tetrahedra,  an edgeedge with one Ti(2)S6 octahedra, and  an edgeedge with one P(1)S3 tetrahedra. The corner-sharing octahedral tilt angles range from 13-61°. 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 P(1)S3 tetrahedra and corners with two equivalent Mg(1)S5 trigonal bipyramids. 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 distorted TiS6 octahedra that share  a cornercorner with one Mg(1)S5 trigonal bipyramid,  an edgeedge with one P(1)S3 tetrahedra, and  an edgeedge with one Mg(1)S5 trigonal bipyramid. There are four inequivalent P sites. In the first P site, P(1) is bonded to one S(11), one S(3), and one S(8) atom to form distorted PS3 tetrahedra that share  a cornercorner with one Ti(1)S6 octahedra,  a cornercorner with one Mg(1)S5 trigonal bipyramid,  an edgeedge with one Ti(2)S6 octahedra, and  an edgeedge with one Mg(1)S5 trigonal bipyramid. The corner-sharing octahedral tilt angles are 73°. In the second P site, P(2) is bonded in a distorted trigonal non-coplanar geometry to one S(1), one S(6), and one S(9) atom. In the third P site, P(3) is bonded in a distorted trigonal non-coplanar 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 an L-shaped geometry to one Ti(1) and one P(2) atom. In the second S site, S(2) is bonded in an L-shaped geometry to 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 T-shaped 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 a distorted T-shaped geometry to one Mg(1), one Ti(2), and one P(4) atom. In the eighth S site, S(8) is bonded in a distorted T-shaped geometry to one Mg(1), one Ti(2), and one P(1) atom. In the ninth S site, S(9) is bonded in an L-shaped geometry to one Ti(1) and one P(2) atom. In the tenth S site, S(10) is bonded in an L-shaped geometry to one Ti(1) and one P(3) atom. In the eleventh S site, S(11) is bonded in a T-shaped geometry to one Mg(1), 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(11), one S(3), one S(4), one S(7), and one S(8) atom to form distorted MgS5 trigonal bipyramids that share  a cornercorner with one Ti(2)S6 octahedra, corners with two equivalent Ti(1)S6 octahedra,  a cornercorner with one P(1)S3 tetrahedra,  an edgeedge with one Ti(2)S6 octahedra, and  an edgeedge with one P(1)S3 tetrahedra. The corner-sharing octahedral tilt angles range from 13-61°. The Mg(1)-S(11) bond length is 2.69 Å. The Mg(1)-S(3) bond length is 2.62 Å. The Mg(1)-S(4) bond length is 2.56 Å. The Mg(1)-S(7) bond length is 2.63 Å. The Mg(1)-S(8) bond length is 2.62 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 P(1)S3 tetrahedra and corners with two equivalent Mg(1)S5 trigonal bipyramids. The Ti(1)-S(1) bond length is 2.45 Å. The Ti(1)-S(10) bond length is 2.45 Å. The Ti(1)-S(2) bond length is 2.45 Å. The Ti(1)-S(3) bond length is 2.64 Å. The Ti(1)-S(4) bond length is 2.60 Å. The Ti(1)-S(9) bond length is 2.47 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 distorted TiS6 octahedra that share  a cornercorner with one Mg(1)S5 trigonal bipyramid,  an edgeedge with one P(1)S3 tetrahedra, and  an edgeedge with one Mg(1)S5 trigonal bipyramid. The Ti(2)-S(11) bond length is 2.66 Å. The Ti(2)-S(12) bond length is 2.63 Å. The Ti(2)-S(5) bond length is 2.39 Å. The Ti(2)-S(6) bond length is 2.38 Å. The Ti(2)-S(7) bond length is 2.55 Å. The Ti(2)-S(8) bond length is 2.59 Å. There are four inequivalent P sites. In the first P site, P(1) is bonded to one S(11), one S(3), and one S(8) atom to form distorted PS3 tetrahedra that share  a cornercorner with one Ti(1)S6 octahedra,  a cornercorner with one Mg(1)S5 trigonal bipyramid,  an edgeedge with one Ti(2)S6 octahedra, and  an edgeedge with one Mg(1)S5 trigonal bipyramid. The corner-sharing octahedral tilt angles are 73°. The P(1)-S(11) bond length is 2.04 Å. The P(1)-S(3) bond length is 2.05 Å. The P(1)-S(8) bond length is 2.05 Å. In the second P site, P(2) is bonded in a distorted trigonal non-coplanar geometry to one S(1), one S(6), and one S(9) atom. The P(2)-S(1) bond length is 2.03 Å. The P(2)-S(6) bond length is 2.07 Å. The P(2)-S(9) bond length is 2.03 Å. In the third P site, P(3) is bonded in a distorted trigonal non-coplanar geometry to one S(10), one S(2), and one S(5) atom. The P(3)-S(10) bond length is 2.03 Å. The P(3)-S(2) bond length is 2.03 Å. The P(3)-S(5) bond length is 2.06 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 1.99 Å. The P(4)-S(4) bond length is 2.07 Å. The P(4)-S(7) bond length is 2.05 Å. There are twelve inequivalent S sites. In the first S site, S(1) is bonded in an L-shaped geometry to one Ti(1) and one P(2) atom. In the second S site, S(2) is bonded in an L-shaped geometry to 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 T-shaped 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 a distorted T-shaped geometry to one Mg(1), one Ti(2), and one P(4) atom. In the eighth S site, S(8) is bonded in a distorted T-shaped geometry to one Mg(1), one Ti(2), and one P(1) atom. In the ninth S site, S(9) is bonded in an L-shaped geometry to one Ti(1) and one P(2) atom. In the tenth S site, S(10) is bonded in an L-shaped geometry to one Ti(1) and one P(3) atom. In the eleventh S site, S(11) is bonded in a T-shaped geometry to one Mg(1), 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.