NaTi2Ga5O12 crystallizes in the orthorhombic Pbam space group. Na(1) is bonded in a 6-coordinate geometry to two equivalent O(3) and four equivalent O(5) atoms. Ti(1) is bonded to one O(1), one O(6), two equivalent O(4), and two equivalent O(5) atoms to form distorted TiO6 octahedra that share corners with two equivalent Ga(1)O6 octahedra, corners with two equivalent Ga(2)O6 octahedra,  a cornercorner with one Ga(3)O4 tetrahedra, edges with two equivalent Ti(1)O6 octahedra, and edges with two equivalent Ga(2)O6 octahedra. The corner-sharing octahedral tilt angles are 50°. There are three inequivalent Ga sites. In the first Ga site, Ga(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form GaO6 octahedra that share corners with four equivalent Ti(1)O6 octahedra, corners with four equivalent Ga(3)O4 tetrahedra, and edges with two equivalent Ga(1)O6 octahedra. The corner-sharing octahedral tilt angles are 50°. In the second Ga site, Ga(2) is bonded to one O(4), one O(5), two equivalent O(3), and two equivalent O(6) atoms to form GaO6 octahedra that share corners with two equivalent Ti(1)O6 octahedra, corners with four equivalent Ga(3)O4 tetrahedra, edges with two equivalent Ti(1)O6 octahedra, and edges with two equivalent Ga(2)O6 octahedra. The corner-sharing octahedral tilt angles are 50°. In the third Ga site, Ga(3) is bonded to one O(3), one O(6), and two equivalent O(2) atoms to form GaO4 tetrahedra that share  a cornercorner with one Ti(1)O6 octahedra, corners with two equivalent Ga(1)O6 octahedra, corners with four equivalent Ga(2)O6 octahedra, and corners with two equivalent Ga(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 56-67°. There are six inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one Ti(1) and two equivalent Ga(1) atoms. In the second O site, O(2) is bonded in a trigonal planar geometry to one Ga(1) and two equivalent Ga(3) atoms. In the third O site, O(3) is bonded to one Na(1), one Ga(3), and two equivalent Ga(2) atoms to form distorted ONaGa3 tetrahedra that share corners with two equivalent O(5)Na2Ti2Ga square pyramids, corners with three equivalent O(3)NaGa3 tetrahedra, and edges with two equivalent O(5)Na2Ti2Ga square pyramids. In the fourth O site, O(4) is bonded in a trigonal planar geometry to two equivalent Ti(1) and one Ga(2) atom. In the fifth O site, O(5) is bonded to two equivalent Na(1), two equivalent Ti(1), and one Ga(2) atom to form distorted ONa2Ti2Ga square pyramids that share corners with two equivalent O(5)Na2Ti2Ga square pyramids, corners with two equivalent O(3)NaGa3 tetrahedra, edges with three equivalent O(5)Na2Ti2Ga square pyramids, and edges with two equivalent O(3)NaGa3 tetrahedra. In the sixth O site, O(6) is bonded in a distorted rectangular see-saw-like geometry to one Ti(1), one Ga(3), and two equivalent Ga(2) atoms.
NaTi2Ga5O12 crystallizes in the orthorhombic Pbam space group. Na(1) is bonded in a 6-coordinate geometry to two equivalent O(3) and four equivalent O(5) atoms. Both Na(1)-O(3) bond lengths are 2.51 Å. All Na(1)-O(5) bond lengths are 2.63 Å. Ti(1) is bonded to one O(1), one O(6), two equivalent O(4), and two equivalent O(5) atoms to form distorted TiO6 octahedra that share corners with two equivalent Ga(1)O6 octahedra, corners with two equivalent Ga(2)O6 octahedra,  a cornercorner with one Ga(3)O4 tetrahedra, edges with two equivalent Ti(1)O6 octahedra, and edges with two equivalent Ga(2)O6 octahedra. The corner-sharing octahedral tilt angles are 50°. The Ti(1)-O(1) bond length is 1.83 Å. The Ti(1)-O(6) bond length is 2.21 Å. Both Ti(1)-O(4) bond lengths are 1.98 Å. Both Ti(1)-O(5) bond lengths are 2.03 Å. There are three inequivalent Ga sites. In the first Ga site, Ga(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form GaO6 octahedra that share corners with four equivalent Ti(1)O6 octahedra, corners with four equivalent Ga(3)O4 tetrahedra, and edges with two equivalent Ga(1)O6 octahedra. The corner-sharing octahedral tilt angles are 50°. Both Ga(1)-O(2) bond lengths are 1.96 Å. All Ga(1)-O(1) bond lengths are 2.01 Å. In the second Ga site, Ga(2) is bonded to one O(4), one O(5), two equivalent O(3), and two equivalent O(6) atoms to form GaO6 octahedra that share corners with two equivalent Ti(1)O6 octahedra, corners with four equivalent Ga(3)O4 tetrahedra, edges with two equivalent Ti(1)O6 octahedra, and edges with two equivalent Ga(2)O6 octahedra. The corner-sharing octahedral tilt angles are 50°. The Ga(2)-O(4) bond length is 1.99 Å. The Ga(2)-O(5) bond length is 2.09 Å. Both Ga(2)-O(3) bond lengths are 1.99 Å. Both Ga(2)-O(6) bond lengths are 2.04 Å. In the third Ga site, Ga(3) is bonded to one O(3), one O(6), and two equivalent O(2) atoms to form GaO4 tetrahedra that share  a cornercorner with one Ti(1)O6 octahedra, corners with two equivalent Ga(1)O6 octahedra, corners with four equivalent Ga(2)O6 octahedra, and corners with two equivalent Ga(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 56-67°. The Ga(3)-O(3) bond length is 1.87 Å. The Ga(3)-O(6) bond length is 1.88 Å. Both Ga(3)-O(2) bond lengths are 1.83 Å. There are six inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one Ti(1) and two equivalent Ga(1) atoms. In the second O site, O(2) is bonded in a trigonal planar geometry to one Ga(1) and two equivalent Ga(3) atoms. In the third O site, O(3) is bonded to one Na(1), one Ga(3), and two equivalent Ga(2) atoms to form distorted ONaGa3 tetrahedra that share corners with two equivalent O(5)Na2Ti2Ga square pyramids, corners with three equivalent O(3)NaGa3 tetrahedra, and edges with two equivalent O(5)Na2Ti2Ga square pyramids. In the fourth O site, O(4) is bonded in a trigonal planar geometry to two equivalent Ti(1) and one Ga(2) atom. In the fifth O site, O(5) is bonded to two equivalent Na(1), two equivalent Ti(1), and one Ga(2) atom to form distorted ONa2Ti2Ga square pyramids that share corners with two equivalent O(5)Na2Ti2Ga square pyramids, corners with two equivalent O(3)NaGa3 tetrahedra, edges with three equivalent O(5)Na2Ti2Ga square pyramids, and edges with two equivalent O(3)NaGa3 tetrahedra. In the sixth O site, O(6) is bonded in a distorted rectangular see-saw-like geometry to one Ti(1), one Ga(3), and two equivalent Ga(2) atoms.