Mg3Ti4P6O24 crystallizes in the triclinic P-1 space group. There are two inequivalent Mg sites. In the first Mg site, Mg(1) is bonded to one O(10), one O(11), one O(12), one O(5), and one O(8) atom to form MgO5 trigonal bipyramids that share  a cornercorner with one Mg(2)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra,  an edgeedge with one Ti(1)O6 octahedra, and  an edgeedge with one Ti(2)O6 octahedra. The corner-sharing octahedral tilt angles are 64°. In the second Mg site, Mg(2) is bonded to two equivalent O(12), two equivalent O(6), and two equivalent O(7) atoms to form MgO6 octahedra that share corners with two equivalent Ti(2)O6 octahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra, and corners with two equivalent Mg(1)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles are 63°. There are two inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to one O(1), one O(11), one O(5), one O(9), and two equivalent O(2) atoms to form TiO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra,  an edgeedge with one Ti(1)O6 octahedra, and  an edgeedge with one Mg(1)O5 trigonal bipyramid. In the second Ti site, Ti(2) is bonded to one O(10), one O(4), one O(6), one O(8), and two equivalent O(3) atoms to form TiO6 octahedra that share  a cornercorner with one Mg(2)O6 octahedra,  a cornercorner with one P(2)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra, corners with three equivalent P(1)O4 tetrahedra,  an edgeedge with one Ti(2)O6 octahedra, and  an edgeedge with one Mg(1)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles are 63°. There are three inequivalent P sites. In the first P site, P(1) is bonded to one O(2), one O(3), one O(7), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one Mg(2)O6 octahedra, corners with two equivalent Ti(1)O6 octahedra, corners with three equivalent Ti(2)O6 octahedra, and  a cornercorner with one Mg(1)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 20-57°. In the second P site, P(2) is bonded to one O(11), one O(12), one O(4), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one Mg(2)O6 octahedra,  a cornercorner with one Ti(2)O6 octahedra, corners with two equivalent Ti(1)O6 octahedra, and corners with two equivalent Mg(1)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 25-58°. In the third P site, P(3) is bonded to one O(1), one O(10), one O(5), and one O(6) atom to form PO4 tetrahedra that share  a cornercorner with one Mg(2)O6 octahedra, corners with two equivalent Ti(1)O6 octahedra, corners with two equivalent Ti(2)O6 octahedra, and corners with two equivalent Mg(1)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 32-61°. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one Ti(1) and one P(3) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to two equivalent Ti(1) and one P(1) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to two equivalent Ti(2) and one P(1) atom. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to one Ti(2) and one P(2) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one Mg(1), one Ti(1), and one P(3) atom. In the sixth O site, O(6) is bonded in a trigonal planar geometry to one Mg(2), one Ti(2), and one P(3) atom. In the seventh O site, O(7) is bonded in a bent 150 degrees geometry to one Mg(2) and one P(1) atom. In the eighth O site, O(8) is bonded in a distorted trigonal planar geometry to one Mg(1), one Ti(2), and one P(1) atom. In the ninth O site, O(9) is bonded in a bent 150 degrees geometry to one Ti(1) and one P(2) atom. In the tenth O site, O(10) is bonded in a distorted trigonal planar geometry to one Mg(1), one Ti(2), and one P(3) atom. In the eleventh O site, O(11) is bonded in a distorted trigonal planar geometry to one Mg(1), one Ti(1), and one P(2) atom. In the twelfth O site, O(12) is bonded in a trigonal planar geometry to one Mg(1), one Mg(2), and one P(2) atom.
Mg3Ti4P6O24 crystallizes in the triclinic P-1 space group. There are two inequivalent Mg sites. In the first Mg site, Mg(1) is bonded to one O(10), one O(11), one O(12), one O(5), and one O(8) atom to form MgO5 trigonal bipyramids that share  a cornercorner with one Mg(2)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra,  an edgeedge with one Ti(1)O6 octahedra, and  an edgeedge with one Ti(2)O6 octahedra. The corner-sharing octahedral tilt angles are 64°. The Mg(1)-O(10) bond length is 2.09 Å. The Mg(1)-O(11) bond length is 2.06 Å. The Mg(1)-O(12) bond length is 2.01 Å. The Mg(1)-O(5) bond length is 2.15 Å. The Mg(1)-O(8) bond length is 2.01 Å. In the second Mg site, Mg(2) is bonded to two equivalent O(12), two equivalent O(6), and two equivalent O(7) atoms to form MgO6 octahedra that share corners with two equivalent Ti(2)O6 octahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra, and corners with two equivalent Mg(1)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles are 63°. Both Mg(2)-O(12) bond lengths are 2.23 Å. Both Mg(2)-O(6) bond lengths are 2.23 Å. Both Mg(2)-O(7) bond lengths are 2.06 Å. There are two inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to one O(1), one O(11), one O(5), one O(9), and two equivalent O(2) atoms to form TiO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra,  an edgeedge with one Ti(1)O6 octahedra, and  an edgeedge with one Mg(1)O5 trigonal bipyramid. The Ti(1)-O(1) bond length is 1.93 Å. The Ti(1)-O(11) bond length is 2.18 Å. The Ti(1)-O(5) bond length is 2.06 Å. The Ti(1)-O(9) bond length is 1.97 Å. There is one shorter (2.08 Å) and one longer (2.16 Å) Ti(1)-O(2) bond length. In the second Ti site, Ti(2) is bonded to one O(10), one O(4), one O(6), one O(8), and two equivalent O(3) atoms to form TiO6 octahedra that share  a cornercorner with one Mg(2)O6 octahedra,  a cornercorner with one P(2)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra, corners with three equivalent P(1)O4 tetrahedra,  an edgeedge with one Ti(2)O6 octahedra, and  an edgeedge with one Mg(1)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles are 63°. The Ti(2)-O(10) bond length is 2.09 Å. The Ti(2)-O(4) bond length is 1.94 Å. The Ti(2)-O(6) bond length is 2.17 Å. The Ti(2)-O(8) bond length is 2.12 Å. There is one shorter (2.07 Å) and one longer (2.09 Å) Ti(2)-O(3) bond length. There are three inequivalent P sites. In the first P site, P(1) is bonded to one O(2), one O(3), one O(7), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one Mg(2)O6 octahedra, corners with two equivalent Ti(1)O6 octahedra, corners with three equivalent Ti(2)O6 octahedra, and  a cornercorner with one Mg(1)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 20-57°. The P(1)-O(2) bond length is 1.58 Å. The P(1)-O(3) bond length is 1.57 Å. The P(1)-O(7) bond length is 1.50 Å. The P(1)-O(8) bond length is 1.56 Å. In the second P site, P(2) is bonded to one O(11), one O(12), one O(4), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one Mg(2)O6 octahedra,  a cornercorner with one Ti(2)O6 octahedra, corners with two equivalent Ti(1)O6 octahedra, and corners with two equivalent Mg(1)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 25-58°. The P(2)-O(11) bond length is 1.57 Å. The P(2)-O(12) bond length is 1.56 Å. The P(2)-O(4) bond length is 1.55 Å. The P(2)-O(9) bond length is 1.53 Å. In the third P site, P(3) is bonded to one O(1), one O(10), one O(5), and one O(6) atom to form PO4 tetrahedra that share  a cornercorner with one Mg(2)O6 octahedra, corners with two equivalent Ti(1)O6 octahedra, corners with two equivalent Ti(2)O6 octahedra, and corners with two equivalent Mg(1)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 32-61°. The P(3)-O(1) bond length is 1.53 Å. The P(3)-O(10) bond length is 1.57 Å. The P(3)-O(5) bond length is 1.57 Å. The P(3)-O(6) bond length is 1.56 Å. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one Ti(1) and one P(3) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to two equivalent Ti(1) and one P(1) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to two equivalent Ti(2) and one P(1) atom. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to one Ti(2) and one P(2) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one Mg(1), one Ti(1), and one P(3) atom. In the sixth O site, O(6) is bonded in a trigonal planar geometry to one Mg(2), one Ti(2), and one P(3) atom. In the seventh O site, O(7) is bonded in a bent 150 degrees geometry to one Mg(2) and one P(1) atom. In the eighth O site, O(8) is bonded in a distorted trigonal planar geometry to one Mg(1), one Ti(2), and one P(1) atom. In the ninth O site, O(9) is bonded in a bent 150 degrees geometry to one Ti(1) and one P(2) atom. In the tenth O site, O(10) is bonded in a distorted trigonal planar geometry to one Mg(1), one Ti(2), and one P(3) atom. In the eleventh O site, O(11) is bonded in a distorted trigonal planar geometry to one Mg(1), one Ti(1), and one P(2) atom. In the twelfth O site, O(12) is bonded in a trigonal planar geometry to one Mg(1), one Mg(2), and one P(2) atom.